Selective deposition on silicon containing surfaces

ABSTRACT

A method is disclosed for delectively depositing a material on a substrate wherein the substrate has at least two different surfaces wherein one surface is passivated thereby allowing selective deposition on the non-passivated surface. In particular, disclosed is a method for preparing a surface of a substrate for selective film deposition, wherein the surface of the substrate comprises at least a first surface comprising SiO 2  and an initial concentration of surface hydroxyl groups and a second surface comprising SiH, the method comprising the steps of: contacting the substrate with a wet chemical composition to obtain a treated substrate comprising an increased concentration of surface hydroxyl groups relative to the initial concentration of surface hydroxyl groups; and heating the treated substrate to a temperature of from about 200° C. to about 600° C., wherein the heating step converts at least a portion of the surface hydroxyl groups on the first surface to surface siloxane groups on the surface of the substrate.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority under 35 U.S.C. § 119(e) to U.S.provisional patent application No. 62/472,724, filed on Mar. 17, 2017,the entirety of which is incorporated herein by reference.

BACKGROUND

The present application relates to selective deposition on a firstsurface of a substrate relative to a second surface. In addition,further processing can be used to subsequently deposit a differentmaterial on the second surface relative to the first.

Selective deposition processes are gaining a lot of momentum mostlybecause of the limitations of contemporary lithographic processes toenable the fabrication of advanced semiconductor devices based on everdiminishing physical dimensions. Traditionally, patterning in themicroelectronics industry has been accomplished using variouslithography and etch processes. However, since lithography is becomingexponentially more complex and expensive the use of selective depositionto form self-aligned features is becoming much more attractive. Thefabrication of self-aligned via structures would benefit significantlyfrom manufacturable selective deposition processes. Another potentialapplication for selective deposition is gap fill. In gap fill, thedielectric “fill” film is grown selectively from the bottom of a trenchtowards the top. Selective deposition could be used for otherapplications such as selective sidewall deposition where films areselectively deposited on exposed surfaces of three dimensional FIN-FETstructures. This would enable the deposition of a sidewall spacerwithout the need for complex patterning steps. Selective depositionprocesses for metal and metal oxide films that are used as gatedielectrics and capacitor dielectrics would also be of great utility insemiconductor device manufacturing.

There are many previous examples within the technical literature relatedto the selective formation of surface passivation coatings on waferswith multiple, different chemical surfaces that are exposed. This hasbeen done with the purpose of retarding or preventing the deposition offilms through ALD processes on these passivated surfaces, but notpreventing deposition on the surfaces where the ALD deposition processis desired to deposit a film. In general, the selectivity of theprocesses has been less than adequate due to incomplete passivation ofthe surfaces and/or due to physisorption of ALD precursor molecules andsubsequent formation of the ALD film material either within thepassivation layer itself or on the surfaces where deposition is notdesired. The present invention seeks to overcome the limitations of theprior art and provide improved methods for selective deposition of thinfilm materials using ALD deposition processes.

SUMMARY

One or more embodiments of the disclosure are directed to methods ofdepositing a film. A substrate comprising a first substrate surfaceincluding a hydroxyl-terminated surface and a second substrate surfaceincluding a hydrogen-terminated surface is provided. The substrate isexposed to multiple processing steps to selectively alter thehydroxyl-terminated surface relative to the hydrogen-terminated surfacein order to render it unreactive, or less reactive, than an untreatedhydroxyl-terminated surface during a subsequent film deposition stepwherein a film is selectively deposited on the hydrogen-terminatedsurface.

In the broadest aspect, the present invention provides a method forpreparing a surface of a substrate for selective film deposition,wherein the surface of the substrate comprises at least a first surfacecomprising SiO₂ and an initial concentration of surface hydroxyl groupsand a second surface comprising SiH, the method comprising the steps of:contacting the substrate to a wet chemical composition to obtain atreated substrate comprising an increased concentration of surfacehydroxyl groups relative to the initial concentration of surfacehydroxyl groups; and heating the treated substrate at a temperature offrom about 200° C. to about 600° C., wherein the heating step convertsat least a portion of the surface hydroxyl groups on the first surfaceto surface siloxane groups on the surface of the substrate.

In another aspect, the present invention provides a method forselectively passivating the surface of a substrate by vapor phasereaction, wherein the surface of the substrate comprises at least afirst surface comprising SiO₂ and an initial concentration of surfacehydroxyl groups and a second surface comprising SiH, the methodcomprising the steps of: contacting the substrate to a wet chemicalcomposition to obtain a treated substrate comprising an increasedconcentration of surface hydroxyl groups relative to the initialconcentration of surface hydroxyl groups; heating the treated substrateat a temperature of from about 200° C. to about 600° C. and a pressureof from 10-10 Torr to 3000 Torr, wherein the heating step converts atleast a portion of the surface hydroxyl groups on the first surface tosurface siloxane groups on the surface of the substrate; exposing thesubstrate, at a temperature equal to or below the heating step, to asilicon-containing compound selected from the group consisting ofFormula I and Formula II:

wherein R¹, R², and R⁴ are each independently selected from H, a C₁ toC₈ linear alkyl group, a branched C₃ to C₈ alkyl group, a C₃ to C₈cyclic alkyl group, a C₃ to C₁₀ heterocyclic group, a C₃ to C₁₀ alkenylgroup, a C₄ to C₈ aryl group, and a C₃ to C₁₀ alkynyl group; R³ isselected from a C₁ to C₁₈ alkyl group, a branched C₃ to C₁₀ alkyl group,a C₄ to C₁₀ heterocyclic group and a C₄ to C₁₀ aryl group; R⁵ isselected from a bond, a C₁ to C₈ linear alkyl group, a branched C₃ to C₈alkyl group, a C₃ to C₈ cyclic alkyl group, a C₃ to C₁₀ heterocyclicgroup, a C₃ to C₁₀ alkenyl group, a C₄ to C₈ aryl group, and a C₃ to C₁₀alkynyl group; X is selected from NR^(a)R^(b), Cl, F, Br, I, —OCH₃, and—OH, wherein R^(a) and R^(b) are each independently selected from H, aC₁ to C₄ linear alkyl group and a C₁-C₄ branched alkyl group; and n andn′ are each independently selected from a number of from 0 to 5, whereinn+n′>1 and <11, wherein the silicon-containing compound reacts with thesurface hydroxyl groups of the first surface to form a silylether-terminated surface and thereby passivate the surface.

In another aspect, the present invention provides a method ofselectively depositing a film on a surface of a substrate wherein thesurface of the substrate comprises at least a first surface comprisingSiO₂ and an initial concentration of surface hydroxyl groups and asecond surface comprising SiH, the method comprising the steps of:contacting the substrate to a wet chemical composition to obtain atreated substrate comprising an increased concentration of surfacehydroxyl groups relative to the initial concentration of surfacehydroxyl groups; heating the treated substrate at a temperature of fromabout 200° C. to about 600° C. and a pressure of from 10-10 Torr to 3000Torr, wherein the heating step converts at least a portion of thesurface hydroxyl groups on the first surface to surface siloxane groupson the surface of the substrate; exposing the substrate, at atemperature equal to or below the heating step, to a silicon-containingcompound selected from the group consisting of Formula I and Formula II:

wherein R¹, R², and R⁴ are each independently selected from H, a C₁ toC₈ linear alkyl group, a branched C₃ to C₈ alkyl group, a C₃ to C₈cyclic alkyl group, a C₃ to C₁₀ heterocyclic group, a C₃ to C₁₀ alkenylgroup, a C₄ to C₈ aryl group, and a C₃ to C₁₀ alkynyl group; R³ isselected from a C₁ to C₁₈ alkyl group, a branched C₃ to C₁₀ alkyl group,a C₄ to C₁₀ heterocyclic group and a C₄ to C₁₀ aryl group; R⁵ isselected from a bond, a C₁ to C₈ linear alkyl group, a branched C₃ to C₈alkyl group, a C₃ to C₈ cyclic alkyl group, a C₃ to C₁₀ heterocyclicgroup, a C₃ to C₁₀ alkenyl group, a C₄ to C₈ aryl group, and a C₃ to C₁₀alkynyl group; X is selected from NR^(a)R^(b), Cl, F, Br, I, —OCH₃, and—OH, wherein R^(a) and R^(b) are each independently selected from H, aC₁ to C₄ linear alkyl group and a C₁-C₄ branched alkyl group; and n andn′ are each independently selected from a number of from 0 to 5, whereinn+n′>1 and <11, wherein the silicon-containing compound reacts with thesurface hydroxyl groups of the first surface to form a silylether-terminated surface and thereby passivate the surface; and exposingthe substrate to one or more deposition gases to deposit a film on thesecond surface selectively over the first surface.

The embodiments of the invention can be used alone or in combinationswith each other.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is an illustration of the effect of the heat treatment step ofthe present invention on a substrate surface;

FIG. 2 is an illustration of a passivated surface according to thepresent invention;

FIG. 3 is a TOF-SIMS spectra of a substrate surface after a wet chemicalexposure step according to an embodiment of the present invention;

FIG. 4 is a graph illustrating the temperature profile verus time for athermal treatment step according to an embodiment of the presentinvention as well as the corresponding QMS spectra showing loss of H₂Osignal;

FIG. 5 is a graph illustrating the normalized intensity of SiOH measuredby TOF-SIMS for a substrate surface pre- and post-thermal exposure;

FIG. 6 is a TOF-SIMS spectra of a substrate surface after a wet chemicalexposure step according to an embodiment of the present invention;

FIG. 7 is a graph illustrating the temperature profile verus time for athermal treatment step according to an embodiment of the presentinvention;

FIG. 8 is a graph illustrating the temperature profile verus time for athermal treatment step according to an embodiment of the presentinvention as well as the corresponding QMS spectra showing loss of H₂Osignal;

FIG. 9 is a series of TOF-SIMS spectra of a substrate surface after awet chemical exposure step and after thermal treatment according to anembodiment of the present invention;

FIG. 10 is a graph illustrating the temperature profile verus time for athermal treatment step according to an embodiment of the presentinvention;

FIG. 11 is a series of TOF-SIMS spectra of a substrate surface asreceived and after a thermal treatment according to an embodiment of thepresent invention;

FIG. 12 is a graph illustrating the temperature profile verus time for athermal treatment step according to an embodiment of the presentinvention as well as the corresponding QMS spectra showing loss of H₂Osignal;

FIG. 13 is a series of TOF-SIMS spectra of a substrate surface after awet chemical exposure step and after thermal treatment according to anembodiment of the present invention;

FIG. 14 is a graph illustrating the temperature profile verus time for athermal treatment step according to an embodiment of the presentinvention;

FIG. 15 is a series of TOF-SIMS spectra of a substrate surface after awet chemical exposure step and after thermal treatment according to anembodiment of the present invention;

FIG. 16 is a graph illustrating the normalized intensity of SiOHmeasured by TOF-SIMS for a substrate surface pre- and post-thermalexposure;

FIG. 17 is a graph plotting the mean contact angles of various substratesurfaces after cleaning, thermal, and passivation steps in embodimentsof the present invention;

FIG. 18 is a graph plotting the mean contact angles of various substratesurfaces after cleaning, thermal, and passivation steps in embodimentsof the present invention;

FIG. 19 is a graph illustrating the temperature profile verus time for athermal treatment step according to an embodiment of the presentinvention;

FIG. 20 is a series of TOF-SIMS spectra of a substrate surface after awet chemical exposure step and after thermal treatment according to anembodiment of the present invention;

FIG. 21 is a series of TOF-SIMS spectra of a substrate surface after awet chemical exposure steps (without thermal treatment) according to anembodiment of the present invention;

FIG. 22 is a graph illustrating the temperature profile verus time for athermal treatment step according to an embodiment of the presentinvention;

FIG. 23 is a series of TOF-SIMS spectra of a substrate surface after awet chemical exposure step and after thermal treatment according to anembodiment of the present invention;

FIG. 24 is a series of TOF-SIMS spectra of a substrate surface after awet chemical exposure steps (without thermal treatment) according to anembodiment of the present invention;

FIG. 25 is a graph illustrating the temperature profile verus time for athermal treatment step according to an embodiment of the presentinvention;

FIG. 26 is a series of TOF-SIMS spectra of a substrate surface asreceived after a thermal treatment and of a substrate after a wetchemical treatment plus thermal treatment according to an embodiment ofthe present invention;

FIG. 27 is a series of TOF-SIMS spectra of a substrate surface asreceived after a thermal treatment and of a substrate after a wetchemical treatment plus thermal treatment according to an embodiment ofthe present invention;

FIG. 28 is a TOF-SIMS spectra of a substrate surface after wet chemicaland thermal treatment according to an embodiment of the presentinvention;

FIG. 29 is a TOF-SIMS spectra of a substrate surface as received plusthermal treatment (no wet chemical exposure) according to an embodimentof the present invention;

FIG. 30 is a TOF-SIMS spectra of a substrate surface after wet chemicalexposure and thermal treatment according to an embodiment of the presentinvention;

FIG. 31 is a graph illustrating the temperature profile verus time for athermal treatment step according to an embodiment of the presentinvention;

FIG. 32 is a series of TOF-SIMS spectra of a substrate surface asreceived after a thermal treatment and of a substrate after a wetchemical treatment plus thermal treatment according to an embodiment ofthe present invention;

FIG. 33 is a series of TOF-SIMS spectra of a substrate surface asreceived without a thermal treatment and of a substrate after a wetchemical treatment also without thermal treatment according to anembodiment of the present invention;

FIG. 34 is a series of TOF-SIMS spectra of a substrate surface asreceived with a thermal treatment and of a substrate after a wetchemical treatment also with thermal treatment according to anembodiment of the present invention;

FIG. 35 is a series of TOF-SIMS spectra of a substrate surface asreceived without a thermal treatment and of a substrate after a wetchemical treatment also without thermal treatment according to anembodiment of the present invention;

FIG. 36 is a graph illustrating the temperature profile verus time for athermal treatment step according to an embodiment of the presentinvention;

FIG. 37 is a series of TOF-SIMS spectra of a substrate surface asreceived with a thermal treatment and of a substrate after a wetchemical treatment also with a thermal treatment according to anembodiment of the present invention; and

FIG. 38 is a series of TOF-SIMS spectra of a substrate surface asreceived without a thermal treatment and of a substrate after a wetchemical treatment also without thermal treatment according to anembodiment of the present invention.

DETAILED DESCRIPTION

All references, including publications, patent applications, andpatents, cited herein are hereby incorporated by reference to the sameextent as if each reference were individually and specifically indicatedto be incorporated by reference and were set forth in its entiretyherein.

The use of the terms “a” and “an” and “the” and similar referents in thecontext of describing the invention (especially in the context of thefollowing claims) are to be construed to cover both the singular and theplural, unless otherwise indicated herein or clearly contradicted bycontext. The terms “comprising,” “having,” “including,” and “containing”are to be construed as open-ended terms (i.e., meaning “including, butnot limited to,”) unless otherwise noted. Recitation of ranges of valuesherein are merely intended to serve as a shorthand method of referringindividually to each separate value falling within the range, unlessotherwise indicated herein, and each separate value is incorporated intothe specification as if it were individually recited herein. All methodsdescribed herein can be performed in any suitable order unless otherwiseindicated herein or otherwise clearly contradicted by context. The useof any and all examples, or exemplary language (e.g., “such as”)provided herein, is intended merely to better illuminate the inventionand does not pose a limitation on the scope of the invention unlessotherwise claimed. No language in the specification should be construedas indicating any non-claimed element as essential to the practice ofthe invention.

Preferred embodiments of this invention are described herein, includingthe best mode known to the inventors for carrying out the invention.Variations of those preferred embodiments may become apparent to thoseof ordinary skill in the art upon reading the foregoing description. Theinventor expects skilled artisans to employ such variations asappropriate, and the inventor intends for the invention to be practicedotherwise than as specifically described herein. Accordingly, thisinvention includes all modifications and equivalents of the subjectmatter recited in the claims appended hereto as permitted by applicablelaw. Moreover, any combination of the above-described elements in allpossible variations thereof is encompassed by the invention unlessotherwise indicated herein or otherwise clearly contradicted by context.

There are a variety of methods that could be used for selectivedepositions. Embodiments of the disclosure are directed to methods thatemploy surface deactivation by taking advantage of the surface chemistryof two different surfaces. Since two different surfaces will havedifferent reactive handles, the differences can be taken advantage of byutilizing molecules that will react with one surface (to deactivate thatsurface) and not react with the other surface.

As used in this specification and the appended claims, the term“substrate” and “wafer” are used interchangeably, both referring to asurface, or portion of a surface, upon which a process acts. It willalso be understood by those skilled in the art that reference to asubstrate can also refer to only a portion of the substrate, unless thecontext clearly indicates otherwise. Additionally, reference todepositing on a substrate can mean both a bare substrate and a substratewith one or more films or features deposited or formed thereon.

A “substrate” as used herein, refers to any substrate or materialsurface formed on a substrate upon which film processing is performedduring a fabrication process. For example, a substrate surface on whichprocessing can be performed include materials such as silicon, siliconoxide, strained silicon, silicon on insulator (SOI), carbon dopedsilicon oxides, silicon nitride, doped silicon, germanium, galliumarsenide, glass, sapphire, and any other materials such as metals, metalnitrides, metal alloys, and other conductive materials, depending on theapplication. Substrates include, without limitation, semiconductorwafers. Substrates may be exposed to a pretreatment process to polish,etch, reduce, oxidize, hydroxylate, anneal and/or bake the substratesurface. In addition to film processing directly on the surface of thesubstrate itself, in the present disclosure, any of the film processingsteps disclosed may also be performed on an underlayer formed on thesubstrate as disclosed in more detail below, and the term “substratesurface” is intended to include such underlayer as the contextindicates. Thus for example, where a film/layer or partial film/layerhas been deposited onto a substrate surface, the exposed surface of thenewly deposited film/layer becomes the substrate surface. What a givensubstrate surface comprises will depend on what films are to bedeposited, as well as the particular chemistry used. In one or moreembodiments, the first substrate surface will comprise a metal, and thesecond substrate surface will comprise a dielectric, or vice versa. Insome embodiments, a substrate surface may comprise certain functionality(e.g., —OH, —NH, etc.).

Likewise, the films that can be used in the methods described herein arequite varied. In some embodiments, the films may comprise, or consistessentially of a metal. Examples of metal films include, but are notlimited to, cobalt (Co), copper (Cu), nickel (Ni), tungsten (W), etc. Insome embodiments, the film comprises a dielectric. Examples include,SiO₂, SiN, HfO₂, etc.

As used in this specification and the appended claims, the terms“reactive gas”, “precursor”, “reactant”, and the like, are usedinterchangeably to mean a gas that includes a species which is reactivewith a substrate surface. For example, a first “reactive gas” may simplyadsorb onto the surface of a substrate and be available for furtherchemical reaction with a second reactive gas.

Embodiments of the disclosure provide methods of selectively depositinga film such as, for example, a metal film, onto one surface of asubstrate over a second surface the same substrate. As used in thisspecification and the appended claims, the term “selectively depositinga film on one surface over another surface”, and the like, means thatone of the first or second surface is passivated to substantiallyprevent deposition on the passivated layer and a film is deposited onthe second (non-passivated) surface. The term “over” used in this regarddoes not imply a physical orientation of one surface on top of anothersurface, rather a relationship of the thermodynamic or kineticproperties of the chemical reaction with one surface relative to theother surface. For example, selectively depositing a cobalt film onto acopper surface over a dielectric surface means that the cobalt filmdeposits on the copper surface and less or no cobalt film deposits onthe dielectric surface; or that the formation of the cobalt film on thecopper surface is thermodynamically or kinetically favorable relative tothe formation of a cobalt film on the dielectric surface.

In some situations it is desirable to selectively deposit a material onone surface of a substrate relative to a second, different surface ofthe same substrate. For example, selective deposition may be used toform capping layers, barrier layers, etch stop layers, sacrificialand/or protective layers or for sealing pores, such as in porous low kmaterials.

Using the processes described herein, in some embodiments a materialcomprising Ni, Ti, Fe, or Co, such as Ni metal, nickel nitride orNiN_(x), cobalt, iron or titanium oxide structures can selectively begrown on SiO₂ based surfaces, and other surfaces as described herein. Asused herein, nickel nitride or NiN_(x) refers to a material comprisingat least some Ni—N bonds.

In some embodiments, a first material, such as a material comprising Ni,Ti, Fe, or Co, such as nickel, nickel nitride or NiN_(x), cobalt, ironor titanium oxide film, may be deposited selectively on one surfacerelative to a second, different surface. For example, a nickel, nickelnitride, cobalt, iron or titanium oxide film can be selectivelydeposited on a low-k insulator surface, for example an oxide or nitridesurface, such as a form of silicon oxide or silicon nitride, relative toa second surface, such as a H-terminated surface of the same substrate.

In some embodiments the surface on which selective deposition occurscomprises an AH_(x)-termination, where A is one or more of N, O or S andx is from 1 to 2. In some embodiments the surface comprisesOH-terminations. In some embodiments the surface is an NH_(x)-terminatedsurface such as a —NH or —NH₂ terminated surface. In some embodimentsthe surface is an SH_(x)-terminated surface.

In some embodiments the first surface is a dielectric surface, such as aSiO₂ surface or silicon oxynitride surface. In some embodiments thefirst surface may comprise silicon oxides, silicon nitrides, siliconoxynitrides, fluorinated silica glass (FSG), carbon doped silicon oxide(SiOC) and/or materials containing more than about 50% silicon oxide. Insome embodiments the first surface comprises OH-groups and may comprise,for example, an alumina (Al₂O₃) surface with —OH surface groups.

In some embodiments the second surface is a —SiH₃, —SiH₂, or —SiHsurface. In some embodiments the second surface is formed by etchingnative oxide of silicon and the second surface comprises Si—H bonds. Insome embodiments the second surface is a pure silicon surface or asilicon(100) oriented surface.

In the broadest aspect, the present invention provides a method forpreparing a surface of a substrate for selective film deposition,wherein the surface of the substrate comprises at least a first surfacecomprising SiO₂ and an initial concentration of surface hydroxyl groupsand a second surface comprising SiH, the method comprising the steps of:contacting the substrate to a wet chemical composition to obtain atreated substrate comprising an increased concentration of surfacehydroxyl groups relative to the initial concentration of surfacehydroxyl groups; and heating the treated substrate at a temperature offrom about 200° C. to about 600° C., wherein the heating step convertsat least a portion of the surface hydroxyl groups on the first surfaceto surface siloxane groups on the surface of the substrate. As usedherein the phrase “surface comprising SiH” includes theAH_(x)-termination as defined above.

In another aspect, the present invention provides a method forselectively passivating the surface of a substrate by vapor phasereaction, wherein the surface of the substrate comprises at least afirst surface comprising SiO₂ and an initial concentration of surfacehydroxyl groups and a second surface comprising SiH, the methodcomprising the steps of: contacting the substrate to a wet chemicalcomposition to obtain a treated substrate comprising an increasedconcentration of surface hydroxyl groups relative to the initialconcentration of surface hydroxyl groups; heating the treated substrateat a temperature of from about 200° C. to about 600° C. and a pressureof from 10-10 Torr to 3000 Torr, wherein the heating step converts atleast a portion of the surface hydroxyl groups on the first surface tosurface siloxane groups on the surface of the substrate; exposing thesubstrate, at a temperature equal to or below the heating step, to asilicon-containing compound selected from the group consisting ofFormula I and Formula II:

wherein R¹, R², and R⁴ are each independently selected from H, a C₁ toC₈ linear alkyl group, a branched C₃ to C₈ alkyl group, a C₃ to C₈cyclic alkyl group, a C₃ to C₁₀ heterocyclic group, a C₃ to C₁₀ alkenylgroup, a C₄ to C₈ aryl group, and a C₃ to C₁₀ alkynyl group; R³ isselected from a C₁ to C₁₈ alkyl group, a branched C₃ to C₁₀ alkyl group,a C₄ to C₁₀ heterocyclic group and a C₄ to C₁₀ aryl group; R⁵ isselected from a bond, a C₁ to C₈ linear alkyl group, a branched C₃ to C₈alkyl group, a C₃ to C₈ cyclic alkyl group, a C₃ to C₁₀ heterocyclicgroup, a C₃ to C₁₀ alkenyl group, a C₄ to C₈ aryl group, and a C₃ to C₁₀alkynyl group; X is selected from NR^(a)R^(b), Cl, F, Br, I, —OCH₃, and—OH, wherein R^(a) and R^(b) are each independently selected from H, aC₁ to C₄ linear alkyl group and a C₁-C₄ branched alkyl group; and n andn′ are each independently selected from a number of from 0 to 5, whereinn+n′>1 and <11, wherein the silicon-containing compound reacts with thesurface hydroxyl groups of the first surface to form a silylether-terminated surface and thereby passivate the surface.

In another aspect, the present invention provides a method ofselectively depositing a film on a surface of a substrate wherein thesurface of the substrate comprises at least a first surface comprisingSiO₂ and an initial concentration of surface hydroxyl groups and asecond surface comprising SiH, the method comprising the steps of:contacting the substrate to a wet chemical composition to obtain atreated substrate comprising an increased concentration of surfacehydroxyl groups relative to the initial concentration of surfacehydroxyl groups; heating the treated substrate at a temperature of fromabout 200° C. to about 600° C. and a pressure of from 10-10 Torr to 3000Torr, wherein the heating step converts at least a portion of thesurface hydroxyl groups on the first surface to surface siloxane groupson the surface of the substrate; exposing the substrate, at atemperature equal to or below the heating step, to a silicon-containingcompound selected from the group consisting of Formula I and Formula II:

wherein W, R², and R⁴ are each independently selected from H, a C₁ to C₈linear alkyl group, a branched C₃ to C₈ alkyl group, a C₃ to C₈ cyclicalkyl group, a C₃ to C₁₀ heterocyclic group, a C₃ to C₁₀ alkenyl group,a C₄ to C₈ aryl group, and a C₃ to C₁₀ alkynyl group; R³ is selectedfrom a C₁ to C₁₈ alkyl group, a branched C₃ to C₁₀ alkyl group, a C₄ toC₁₀ heterocyclic group and a C₄ to C₁₀ aryl group; R⁵ is selected from abond, a C₁ to C₈ linear alkyl group, a branched C₃ to C₈ alkyl group, aC₃ to C₈ cyclic alkyl group, a C₃ to C₁₀ heterocyclic group, a C₃ to C₁₀alkenyl group, a C₄ to C₈ aryl group, and a C₃ to C₁₀ alkynyl group; Xis selected from NR^(a)R^(b), Cl, F, Br, I, —OCH₃, and —OH, whereinR^(a) and R^(b) are each independently selected from H, a C₁ to C₄linear alkyl group and a C₁-C₄ branched alkyl group; and n and n′ areeach independently selected from a number of from 0 to 5, wherein n+n′>1and <11, wherein the silicon-containing compound reacts with the surfacehydroxyl groups of the first surface to form a silyl ether-terminatedsurface and thereby passivate the surface; and exposing the substrate toone or more deposition precursors to deposit a film on the secondsurface selectively over the first surface.

In each method disclosed herein, there is provided a method forpreparing a surface of a substrate for selective deposition by vaporphase reaction, wherein the surface comprises SiO₂ and SiH, wherein thefirst step is typically but optionally contacting the surface with a wetchemical composition.

In some embodiments the surface comprising SiO₂ is a dielectric surface,such as a SiO₂ surface and/or silicon oxynitride surface. In someembodiments the surface comprising SiO₂ may comprise silicon oxides,silicon nitrides, silicon oxynitrides, fluorinated silica glass (FSG),carbon doped silicon oxide (SiOC) and/or materials containing more thanabout 50% silicon oxide. In some embodiments the surface comprising SiO₂comprises —OH groups and may comprise, for example, an alumina (Al₂O₃)surface with —OH surface groups.

In some embodiments the surface comprising SiH is a —SiH₃, —SiH₂, or—SiH surface. In some embodiments the surface comprising SiH is a puresilicon surface or an Si(100) surface.

As stated above, the first surface comprises an initial concentration ofsurface hydroxyl groups. Typically, the concentration of surfacehydroxyl groups can be quantified by techniques well known in the artsuch as, for example, Time-of-Flight Secondary Ion Mass Spectrometry(TOF-SIMS). In preferred embodiments, the initial concentration ofsurface hydroxyl groups is from about 1.4×10⁶ normalized counts forpositive ion analysis for mass 45 amu to about 2.2×10⁶ normalized countsfor positive ion analysis for mass 45 amu as determined by TOF-SIMS.This corresponds to hydroxyl surface concentrations of about 4.2 OH/nm²to 4.6 OH/nm² as measured by FTIR and other techniques known to thoseskilled in the art.

The method of the present invention includes the optional step ofcontacting the substrate with a wet chemical composition to obtain atreated substrate comprising an increased concentration of surfacehydroxyl groups relative to the initial concentration of surfacehydroxyl groups. Although optional, it is preferred that the surface ofthe substrate first be treated with a wet chemical treatment. Exemplarywet chemical treatments include known chemical treatments such as, forexample, RCA clean chemicals SC-1 and SC-2, HF, peroxide, H₂SO₄/H₂O₂,NH₄OH, buffered HF solutions, and mixtures thereof.

As is known in the art, “RCA clean chemicals” refer to compositionscomprising an ammonium hydroxide and hydrogen peroxide mixture whereinthe basic cleaning procedure developed by the Radio Corporation ofAmerica in the 1960s. The RCA Standard-Clean-1 (SC-1) procedure uses anammonium hydroxide and hydrogen peroxide solution and water heated to atemperature of about 70° C. The SC-1 procedure dissolves films andremoves Group I and II metals. The Group I and II metals are removedthrough complexing with the reagents in the SC-1 solution. The RCAStandard-Clean-2 (SC-2) procedure utilizes a mixture of hydrogenperoxide, hydrochloric acid, and water heated to a temperature of about70° C. The SC-2 procedure removes the metals that are not removed by theSC-1 procedure.

The purpose of the wet chemical clean is two-fold. First, the wetchemical step removes impurities from the surface to remove the thinoxide grown on the Si (100) surfaces and replaces it with hydrogentermination while preserving to a large extent the —OH surfacetermination on the SiO₂ surfaces. Such processes are common within theindustry and can be optimized to yield clean surfaces with the desiredproperties using methods known to those skilled in the art. Next, thewet chemical clean also increases the concentration of surface hydroxylgroups relative to the concentration of surface hydroxyl groups prior tocontacting the surface with the wet chemical. Preferably, theconcentration of surface hydroxyl groups increases by from about 1.1times the initial concentration to about 1.8 times the initialconcentration and ultimately reaches a surface hydroxyl concentrationthat approaches about 4.6 OH/nm².

Contacting with the wet chemical can occur by any method known to thoseskilled in the art such as, for example, dipping or spraying. Thecontacting step can be one discrete step or more than one step.

In some embodiments, the temperature of the wet chemical during thecontacting step can be, for example, from about 50° C. to about 100° C.In other embodiments, the temperature of the wet chemical during thecontacting step can be, for example, from about 55° C. to about 95° C.In other embodiments, the temperature of the wet chemical during thecontacting step can be, for example, from about 60° C. to about 90° C.

Any process that can be used alone or in conjunction with the wetchemical to increase the surface hydroxyl concentration of the twosubstrate surfaces to a range approaching at least about 3×10¹⁸ OHgroups/m², can be utilized to provide a fully hydroxylated surface,particularly those that simultaneously provide a hydrogen terminatedSi(100) surface. Suitable processes include plasma processes (hydrogenplasma, NH₃/NF₃ plasmas, water plasmas, water/hydrogen peroxide plasmasand the like), wet chemical processes and/or combinations of theforegoing (to provide full hydroxylation of both surfaces, followed bySiH surface formation on the Si(100) surfaces).

The method of the present invention also includes the step of heatingthe treated substrate at a temperature of from about 200° C. to about600° C. and, preferably, from about 200° C. to about 500° C., whereinthe heating step converts at least a portion of the surface hydroxylgroups on the first surface to surface siloxane groups on the surface ofthe substrate. This thermal “treatment” of the wet chemical-cleanedsurface can comprise one step or multiple steps. In the multiple stepembodiment, the thermal treatment may be conducted at one or morediscrete process temperatures for pre-determined lengths of time. Thethermal treatments may be carried out over the temperature range of fromabout 50-1200° C., the pressure range 10-10 Torr to 3000 Torr, with orwithout the presence of a carrier/purge gas for times ranging from 10 sto 12 hours. Any of the process parameters might be changed in apre-determined fashion for a pre-determined length of time during eithera single step thermal treatment or during any of the sub-steps in amulti-step thermal treatment. Heating can be achieved through thermalcontact with a heated surface, use of a heated gas stream, throughradiant heating (i.e., lamps) or through any other suitable means.Heating may be conducted in a dedicated, interconnected chamber that isa part of a multi-chamber cluster tool. Where multiple, discrete heatingsteps are used, they may be carried out in multiple dedicated chambersincluding load locks and heating chambers that may also be part oflarger, interconnected cluster tools.

In one embodiment, the heating step is performed at a temperature offrom about 200° C. to about 600° C. In another embodiment, the heatingstep is performed at a temperature of from about 300° C. to about 550°C. In yet another embodiment, the heating step is performed at atemperature of from about 400° C. to about 500° C. In still anotherembodiment, the heating step is performed by first heating the substrateto a temperature of less than about 200° C. for 5-10 minutes, followedby increasing the temperature to from about 400° C. to about 500° C.

Although described as a two-step process herein, it may be possible toachieve similar results using a single step process carried out at aninitially higher temperature within the range disclosed in the secondstep below. In the first step of the thermal process, adsorbed moistureis removed from the surface of the SiO₂ to prevent the formation ofundesirable interfacial phases during film deposition in a subsequentstep and to help provide a very repeatable hydroxyl concentration on thesurfaces of the exposed SiO₂ films. This first, discrete thermaltreatment may be carried out over the temperature range of from about 50to about 250° C., over the pressure range 10-10 MIT to 760 Torr forlengths of time varying from 1 s to 12 hours. Preferably, thetemperature is between about 50 and about 240° C., the pressure isbetween 10-5 Torr and 300 Torr and the time is between 30 s and 8 hours.Still more preferably, the temperature is between about 50 and about230° C., the pressure is between 10-4 and 100 Torr and the time isbetween 1 minute and 6 hours. The conditions of the first step to removeadsorbed moisture can be routinely optimized using methods known tothose skilled in the art.

Without intending to be bound by a particular theory, it is believedthat during the heating step a portion of the ‘bound’ surface hydroxylgroups are converted to surface siloxane bonds by continued heating atelevated temperature through removal of water molecules from the surface(condensation of surface silanol groups). This second, discrete thermaltreatment may be carried out over the temperature range of from about200 to about 1000° C., over the pressure range 10-10 Torr to 760 Torrfor lengths of time varying from 10 s to 12 hours.

In one example, the temperature of the heating step is between about 280and about 650° C., the pressure is between 10-5 Torr and 300 Torr andthe time is between 30 s and 10 hours. In another example, thetemperature is between about 300 and about 550° C., the pressure isbetween 10-4 and 100 Torr and the time is between 1 minute and 8 hours.The process can be routinely optimized to yield a post thermal treatmentsurface hydroxyl coverage that provides a mean hydroxyl spacing equal tothat desired within the range of from about 3 to 9 Å using methods knownto those skilled in the art.

Referring to FIG. 1 , the function of the thermal treatment is, at leastin part, to remove a portion of the hydroxyl groups from the surfacecomprising the hydroxyl groups. The thermal treatment step(s) may becarried out in any one of several desirable fashions, or through acombination of more than one of them. These include dynamic processingconditions in which the sample is continuously exposed to vacuum with orwithout a flow of carrier/purge gas; static processing conditions inwhich the sample is isolated from the vacuum source for pre-determinedlengths of time with or without a carrier/purge gas present; andpump-purge process conditions in which the sample is pumped oncontinuously for a pre-determined amount of time, then isolated from thevacuum source and the chamber volume containing it is backfilled with anultra-high purity carrier gas to a pre-determined pressure for apre-determined length of time, after which the sample volume is pumpeddown to base vacuum for a pre-determined amount of time. This pump-purgeor cycle purge process may be completed as many times as desired inorder to achieve the desired surface hydroxyl concentration. Routineexperimentation can be used to determine the optimal process conditionsto repeatably yield the desired surface hydroxyl concentration and meanhydroxyl group spacing.

Although described in terms of single and two-step processes, multi-stepprocesses involving as many discrete steps as desired withpre-determined process conditions and pre-determined lengths of time arealso within the scope of the present invention.

The above described steps of contacting the substrate with a wetchemical composition to obtain a treated substrate comprising anincreased concentration of surface hydroxyl groups relative to theinitial concentration of surface hydroxyl groups; and heating thetreated substrate to a temperature of from about 200° C. to about 600°C., wherein the heating step converts at least a portion of the surfacehydroxyl groups on the first surface to surface siloxane groups on thesurface of the substrate provide the basis for the next step in theprocess which is passivating the first surface so that a layer can beselectively deposited on the second surface.

Although presented in the context of producing passivation coatings, theteachings herein can also be readily applied to film depositionconditions through the appropriate choice of deposition precursormolecules and film deposition process conditions (temperature, pressure,partial pressure(s) and duration, coupled with purge conditions (P, T,purge gas and duration) for ALD-like processes) to enable improveddeposition conditions for Si-containing substrate surfaces that compriseSi, O, C, N, H and combinations of the foregoing, including dopants suchas, for example, boron, phosphorous, arsenic, and antimony. Theseprocesses might be selective by incorporating the teachings herein, ornon-selective with regard to film deposition and substrate chemicaltopography. By providing an improved starting SiO₂ surface with reducedsteric hindrance and higher reactivity using the methods disclosedherein, many film deposition processes can be improved. Althoughpresented in the specific case of SiO₂, pre-treatments of other surfacesusing similar techniques as described herein may also improve filmdeposition on those surfaces at low deposition temperatures.

Although described in terms of the SiO₂/Si (100) system, the thermaltreatment step can be utilized for many additional materials to enableselective passivation and/or activation of the desired surfaces andthereby enable selective film deposition processes. The chemical surfaceterminations present on Si(100), Si-containing dielectrics and othermaterials can be similarly altered through the use of appropriateprecursor chemicals and appropriate processing to enable selectivedeposition through selective surface activation/passivation.

In some embodiments, the method of the present invention includes thestep of exposing the substrate, at a temperature equal to or below theheating step, to a silicon-containing compound selected from the groupconsisting of Formula I and Formula II:

wherein R¹, R², and R⁴ are each independently selected from H, a C₁ toC₈ linear alkyl group, a branched C₃ to C₈ alkyl group, a C₃ to C₈cyclic alkyl group, a C₃ to C₁₀ heterocyclic group, a C₃ to C₁₀ alkenylgroup, a C₄ to C₈ aryl group, and a C₃ to C₁₀ alkynyl group; R³ isselected from a C₁ to C₁₈ alkyl group, a branched C₃ to C₁₀ alkyl group,a C₄ to C₁₀ heterocyclic group and a C₄ to C₁₀ aryl group; R⁵ isselected from a bond, a C₁ to C₈ linear alkyl group, a branched C₃ to C₈alkyl group, a C₃ to C₈ cyclic alkyl group, a C₃ to C₁₀ heterocyclicgroup, a C₃ to C₁₀ alkenyl group, a C₄ to C₈ aryl group, and a C₃ to C₁₀alkynyl group; X is selected from NR^(a)R^(b), Cl, F, Br, I, —OCH₃, and—OH, wherein R^(a) and R^(b) are each independently selected from H, aC₁ to C₄ linear alkyl group and a C₁-C₄ branched alkyl group; and n andn′ are each independently selected from a number of from 0 to 5, whereinn+n′>1 and <11, wherein the silicon-containing compound reacts with thesurface hydroxyl groups of the first surface to form a silylether-terminated surface and thereby passivate the surface.

In another embodiment, the compounds for use in the method of thepresent invention are selected from the group consisting of Formula Iand Formula II:

wherein R¹, R², and R⁴ are each independently selected from H, a C₁ toC₁₈ linear alkyl group, a branched C₃ to C₈ alkyl group, a C₃ to C₁₈cyclic or bicyclic alkyl group, a C₃ to C₁₈ heterocyclic group, a C₃ toC₁₈ alkenyl group, a C₄ to C₈ aryl group, and a C₃ to C_(M) alkynylgroup; R³ is selected from a C₁ to C₁₈ alkyl group, a branched C₃ to C₁₀alkyl group, a C₄ to C₁₀ heterocyclic group and a C₄ to C₁₀ aryl group;R⁵ is selected from a bond, a C₁ to C₁₈ linear alkyl group, a branchedC₃ to C₁₈ alkyl group, a C₃ to C₁₈ cyclic or bicyclic alkyl group, a C₃to C₁₀ heterocyclic group, a C₃ to C₁₈ alkenyl group, a C₄ to C₈ arylgroup, and a C₃ to C₁₀ alkynyl group; X is selected from NR^(a)R^(b),Cl, F, Br, I, —OCH₃, and —OH, wherein R^(a) and R^(b) are eachindependently selected from H, a C₁ to C_(a) linear alkyl group and aC₁-C₄ branched alkyl group; and n and n′ are each independently selectedfrom a number of from 0 to 5, wherein n+n′>1 and <11.

As shown above, there are two general classes of silicon-containingprecursor molecules represented by the structures of Formula I andFormula II that may be employed for passivation of SiO₂. Each class ofcompounds are designed to bond to the surface hydroxyl groups through asingle reactive ligand (halogeno, amino, alkoxy or silanol), as opposedto many of the precursors in the prior art that rely on multiplereactive ligands (i.e., trialkoxy or trichloro species). It is presentlybelieved that the single reactive ligand species of the presentinvention will have a high propensity to form monolayer passivationlayers with higher overall surface coverage, particularly in light ofthe surface hydroxyl distribution on the SiO₂ surfaces that will beprovided herein after the thermal treatment step. All are based upon theconcept that the Si—O—Si bond will be the most advantageous in terms ofanchoring the passivation molecule to the surface of the SiO₂ and, thus,the atoms that incorporate the reactive ligand are all Si for thepresent description of the SiO₂/Si (100) system.

The two general ‘classes’ of precursor molecules include those with:

Formula I—One anchor atom to bond to the surface (monopodal molecules);and

Formula II—Two anchor atoms to bond to the surface (bipodal molecules)

Additional embodiments also include the use of fluorocarbon ligands withthe caveat that they include at least one hydrocarbon (CH₂) link bondeddirectly to the silicon atom, thereby separating the silicon atom fromdirect bonding with the fluorocarbon portion of the ligand (i.e. thereare no Si—CF_(x) bonds present within the molecule that will form thesurface passivation layer). Specific, non-limiting examples include iodotris(3,3,3-trifluoropropyl) silane, dimethylaminotris(3,3,3-trifluoropropyl) silane, [(CF₃CF₂(CH₂)₆(CH₃)₂SiCl] and bromotris(1,1,1-3,3,3-hexafluoro-isopropyl) silane.

Specific examples of compounds according to Formula I include, but arenot limited to the following:

A. Trimethylsilicon chloride; trimethylsilicon bromide; trimethylsiliconIodide; dimethylaminotrimethyl silane; ethylmethylaminotrimethyl silane;diethylaminotrimethyl silane; ethylpropylaminotrimethyl silane;di-propylaminotrimethyl silane; ethylisopropylaminotrimethyl silane;di-iso-propylaminotrimethyl silane; di-n-butyltrimethyl silane;di-isobutyltrimethyl silane; di-sec-butyltrimethyl silane;

B. Triethylsilicon chloride; triethylsilicon bromide; triethylsiliconiodide; dimethylaminotriethyl silane; ethylmethylaminotriethyl silane;diethylaminotriethyl silane; ethylpropylaminotriethyl silane;di-propylaminotriethyl silane; ethylisopropylaminotriethyl silane;di-iso-propylaminotriethyl silane; di-n-butyltriethyl silane;di-isobutyltriethyl silane; di-sec-butyltriethyl silane;

C. Tri-n-propylsilicon chloride; tri-n-propylsilicon bromide;tri-n-propylsilicon iodide; dimethylaminotri-n-propyl silane;ethylmethylaminotri-n-propyl silane; diethylaminotri-n-propyl silane;ethylpropylaminotri-n-propylsilane; di-propylaminotri-n-propyl silane;ethylisopropylaminotri-n-propyl silane; di-iso-propylaminotri-n-propylsilane;

D. Tri-isopropylsilicon chloride; tri-isopropylsilicon bromide;tri-isopropylsilicon iodide; dimethylaminotri-isopropyl silane;ethylmethylamino tri-isopropyl silane; diethylamino tri-isopropylsilane; ethylpropylaminotri-isopropyl silane; di-propylaminotri-isopropyl silane; ethylisopropylamino tri-isopropyl silane;di-iso-propylamino tri-isopropyl silane;

E. Tri-n-butylsilicon chloride; Tri-n-butylsilicon bromide;Tri-n-butylsilicon iodide; dimethylaminotri-n-butyl silane;ethylmethylamino tri-n-butyl silane; diethylamino tri-n-butyl silane;

F. Tri-isobutylsilicon chloride; tri-isobutylsilicon bromide;tri-isobutylsilicon iodide; dimethylaminotri-isobutyl silane;ethylmethylamino tri-isobutyl silane; diethylamino tri-isobutyl silane;

G. Tri-secbutylsilicon chloride; tri-secbutylsilicon bromide;tri-secbutylsilicon iodide; dimethylaminotri-secbutyl silane;ethylmethylamino tri-secbutyl silane; diethylamino tri-secbutyl silane;

H. Tri-n-pentylsilicon chloride; tri-n-pentylsilicon bromide;tri-n-pentylsilicon iodide; dimethylaminotri-n-pentyl silane;

I. Chloro-tris(3,3,3-trifluoropropyl)silane;bromo-tris(3,3,3-trifluoropropyl)silane;iodo-tris(3,3,3-trifluoropropyl)silane;dimethylamino-tris(3,3,3-trifluoropropyl)silane;ethylmethylamino-tris(3,3,3-trifluoropropyl)silane;diethylamino-tris(3,3,3-trifluoropropyl)silane;ethylpropylamino-tris(3,3,3-trifluoropropyl)silane;di-propylamino-tris(3,3,3-trifluoropropyl)silane;ethylisopropylamino-tris(3,3,3-trifluoropropyl)silane;di-iso-propylamino-tris(3,3,3-trifluoropropyl)silane;

J. Chloro-tris(4,4,4-trifluorobutyl)silane;bromo-tris(4,4,4-trifluorobutyl)silane;iodo-tris(4,4,4-trifluorobutyl)silane;dimethylamino-tris(4,4,4-trifluorobutyl)silane;

K. Octyldimethylsilicon chloride; octyldimethylsilicon bromide;octyldimethylsilicon iodide; dimethylaminooctyldimethyl silane;

L. Decyldimethylsilicon chloride; Decyldimethylsilicon bromide;Decyldimethylsilicon iodide; dimethylamino Decyldimethyl silane;

M. Dodecyldimethylsilicon chloride; Dodecyldimethylsilicon bromide;Dodecyldimethylsilicon iodide; dimethylaminododecyldimethyl silane;

N. Hexadecyldimethylsilicon chloride; Hexadecyldimethylsilicon bromide;Hexadecyldimethylsilicon iodide; dimethylaminohexadecyldimethyl silane;

O. Octadecyldimethylsilicon chloride; Octadecyldimethylsilicon bromide;Octadecyldimethylsilicon iodide; dimethylamino-octadecyldimethyl silane;

P. Chlorodimethyl(1H,1H-2H,2H-perfluorooctyl)silane;bromodimethyl(1H,1H-2H,2H-perfluorooctyl)silane;iododimethyl(1H,1H-2H,2H-perfluorooctyl)silane;dimethylaminodimethyl(1H,1H-2H,2H-perfluorooctyl)silane;

Q. Chlorodimethyl(1H,1H-2H,2H-perfluorodecyl)silane;bromodimethyl(1H,1H-2H,2H-perfluorodecyl)silane;iododimethyl(1H,1H-2H,2H-perfluorodecyl)silane;dimethylamino-dimethyl(1H,1H-2H,2H-perfluorodecyl)silane; and

R. Chlorodimethyl(1H,1H-2H,2H-perfluorododecyl)silane;bromodimethyl(1H,1H-2H,2H-perfluorododecyl)silane;iododimethyl(1H,1H-2H,2H-perfluorododecyl)silane;dimethylamino-dimethyl(1H,1H-2H,2H-perfluorododecyl)silane.

Specific examples of compounds according to Formula II and II(a)include, but are not limited to the following1,3-bis-chlorodimethylsilyl(ethane); 1,3-bis-bromodimethylsilyl(ethane);1,3-bis-iododimethylsilyl(ethane);1,3-bis-dimethylamino-dimethylsilyl(ethane);1,3-bis-chlorodimethylsilyl(propane);1,3-bis-bromodimethylsilyl(propane); 1,3-bis-iododimethylsilyl(propane);1,3-bis-dimethylamino-dimethylsilyl(propane);1,3-bis-chlorodimethylsilyl(butane); 1,3-bis-bromodimethylsilyl(butane);1,3-bis-iododimethylsilyl(butane); and1,3-bis-dimethylamino-dimethylsilyl(butane).

Additional embodiments also include the use of fluorocarbon ligands inany desired R group position with the caveat that they include at leastone hydrocarbon (CH₂) link bonded directly to the silicon atom, therebyseparating the silicon atom from direct bonding with the fluorocarbonportion of the ligand (i.e., there are no Si—CF_(x) bonds present withinthe molecule that will form the surface passivation layer).

A benefit of the method of the present invention is that one can controlthe surface density of —OH groups by heating the surface as detailedabove after wet chemical treatment. The heat will drive off a portion ofthe —OH groups. This surface density can be measured by, for example,low energy ion scattering, TOF-SIMS, or FTIR (surface mode), and, fromthat information, a precursor can be selected for optimal passivationbased on the size of the precursor. For example, if the distancesbetween —OH groups is about 6.5 Å, then, for example, a bipodalprecursor with ethyl (“(CH₂)₂”) or propyl ((“(CH₂)₃”) linkage may be agood “fit” because the length of a propyl group is about 6.9 Å.

Without intending to be bound by any particular theory, it is believedthat optimal passivation results for SiO₂ dielectric surfaces can beachieved through a combination of thermal treatment processing andpassivation molecule design. Specifically, it is presently believed thatremoval of adsorbed moisture and tightly clustered surface hydroxylgroups from the SiO₂ surface will yield a surface hydroxyl populationthat is largely free of hydrogen bonding, an increased number of surfacesiloxane-like (Si—O—Si) bonds that are far less reactive than hydroxylgroups (and that also have less polarity than —OH surface bonds) andthat can be tailored to have a mean separation distance that can becontrolled through the pre-treatment process conditions. It is believedthat this surface will allow essentially complete passivation ofreactive chemical sites through the use of specific passivationmolecules that have intramolecular lengths that match their reactivegroup distances to the hydroxyl group surface spacing.

The ability to design molecules with the desired/designed spacing ofgroups from both steric hindrance and a reactive ligand spacingperspectives provides a marked improvement over the prior art. It maylead to much faster gas phase surface passivation coating formationreactions and, simultaneously, improved surface coverage (limited onlyby the inherent ‘steric crowding’ imparted by the choice of organicligands incorporated into the parent passivation molecule). For thespecific embodiment of selective passivation of a SiO₂ surface relativeto a Si(100) surface the thermal pre-treatment temperature is preferablybetween from about 375 to about 450° C. in order to provide a meansurface hydroxyl spacing of approximately 6.5 angstroms while leavingthe H-terminated Si(100) surface provided by the initial wet cleaningsteps intact and essentially unchanged. The preferred precursormolecules for this surface depend upon whether they have 1 or 2 pointsof surface bonding embedded within the molecule (i.e., 1 or 2 reactiveligands with no more than 1 reactive ligand attached to any given atomwithin a precursor molecule). For 1 point of surface bonding molecules,the spacing is largely driven by steric hindrance constraints and thenon-reactive ligand(s) are selected such that they will not hinderreactions at neighboring ‘free’ hydroxyl sites, but such that they willprovide maximum surface coverage by organic functionalities. For dipodalpoint of surface bonding molecules, the spacing between the two (singlereactive ligand) atoms is made to be slightly larger than the meanspacing between surface hydroxyl groups.

The controlled “free” surface hydroxyl spacing, coupled with themolecular design may enable rapid and complete, vapor phase formation ofsurface passivation coatings. This represents a potential markedimprovement over the prior art and may result in commercially feasibleselective ALD processes for SiO₂/Si surfaces.

Additional advantages include: (1) that the increased reactivity of the“free” hydroxyl groups enables the use of a wider range of reactiveligands to attach the surface passivation moieties to the SiO₂ surfacesrelative to SiO₂ surfaces not so prepared (i.e., enables the use of abroader range of precursor chemistries); (2) that the passivation layerthat is formed will be formed more rapidly and more completely atreaction temperatures higher than the minimum reaction temperature withbetter (maximized) surface coverage relative to related-art surfaces notso prepared; (3) formation of SiO₂ passivated surfaces with improvedresistance to precursor nucleation in subsequent ALD film depositionprocesses by virtue of the closest-packed passivation layer and thereduction in the number of residual surface hydroxyl bonds (presentbeneath the surface passivation layer for SiO₂ surfaces of the priorart) enabling improved selective film deposition in subsequent processsteps.

It is preferred that the passivation layer be formed as soon as possibleafter heat treatment to avoid exposure of the treated surfaces tomoisture or oxygen.

When used as co-reactants or catalysts, amines are meant to encompassthe class of molecules including NR₃ where R is independently H, alkyl,aryl, alkene, etc. and pyridine and pyridine derivatives. It is known inthe art that amines can be used in conjunction with moleculesencompassing halogen reactive groups to achieve lower overall reactiontemperature for reactions on the hydroxylated surfaces of the relatedart. If used in conjunction with the teachings of the present invention,such amines might enable even lower temperature reactions to form thedesired passivation layers, as well as reduced reaction times. Absentthe teachings of the present invention, the use of these molecules canenable the formation of the desired passivation layers at lowertemperatures than in their absence. In all cases where amineco-reactants are utilized, there is the risk of contamination andpoisoning of the hydroxylated surface through the formation of condensedpyridinium or ammonium halide salts. Care must be used in processdevelopment to minimize the contamination of the hydroxylated surfacesby these salts using methods known to those skilled in the art.

Vapor phase reactions are meant to imply that the precursors are exposedto the heated and pre-treated substrate (that is contained in a sealedvessel) through introduction of the precursors in the vapor phase, butthis does not preclude condensation of precursors or co-reactants on thesurface of the substrate if the substrate temperature is below theboiling point of the precursors and/or co-reactants (i.e. a liquid layermay be allowed to form to promote the reaction of the surface hydroxylgroups with the precursors and/or reactants).

Liquid (solution) phase reactions are meant to imply that the precursorsand/or co-reactants are introduced directly onto the surface of thesubstate in the liquid state, either ‘neat’ or in conjunction with asuitable liquid solvent. If a solvent is used, it should be ultra-highpurity and non-reactive with either the substrate or the precursorsand/or co-reactants.

Vapor phase or gas phase reactions include those between the surfacehydroxyl groups provided by the passivation step and the single reactiveligand on the precursor molecule. They include the exposure of theheated substrate to the precursor molecule(s) and/or co-reactants in asuitable chamber that must be capable of providing the necessarypressure control and that can also supply heat to the substrate and/orchamber walls; the chamber should also provide suitable purity for thereactions that will take place, generally through high leak integrityand the use of ultra-high purity carrier and reactive gases. Anotherembodiment of the invention relates to using cooling of the substrate topromote the formation of a liquid layer of precursor(s) and/orco-reactants on the surface of the substrate prior to subsequentlyheating the substrate to react the precursor(s) and/or co-reactants withthe surface hydroxyl groups.

The term “precursors” is intended to mean the single reactive ligand,single anchor point and/or two anchor point molecules describedpreviously herein. They may be used in conjunction with ultra-highpurity carrier gases (as defined previously) and in any desired mixtureswith one another (i.e. more than one type of precursor can be usedeither together or in discrete, independent steps to form the desiredpassivation layer with whatever order of precursor introduction isdesired). Co-reactants are meant to mean the catalytic amine reactantsdisclosed previously (if they are to be used).

The precursor(s) and/or co-reactants may be delivered to the reactorusing mass flow controllers (perhaps with heated lines), liquidinjection vaporizers (perhaps with heated lines) or with no meteringdevice (i.e. neat introduction of the vapor and or gas from a vesselthat is isolated from the reactor using a simple valve). Any of theforegoing may also be used in combination with one another. Any means ofproviding the gas and/or vapor(s) to the reaction chamber that providessufficient purity and repeatability may be used.

The precursor(s) and/or co-reactants may be introduced independently tothe reactor, mixed prior to introduction to the reactor, mixed in thereactor or in any combination of the preceding in multiple, independentsteps that might include differences in how the precursors areintroduced between steps.

For direct vapor phase reactions, it is believed that the temperaturerange for reaction should be selected to be near the maximum stabilitytemperature of a given surface passivation layer (as mentionedpreviously). However, the temperature range of the reactions may bebetween room temperature and 700° C., with the caveat that thetemperature should be equal to or less than that of the pre-treatmenttemperature. The pressure may range from 10-10 Torr to 3000 Torr and maybe maintained under dynamic flow conditions (i.e. with a valve and abutterfly valve type arrangement) or may be maintained under staticconditions (i.e. an evacuated chamber is exposed to the desiredprecursor(s) and/or co-reactant(s) until a total desired pressure isachieved and then the chamber is isolated from both the precursor(s)and/or co-reactant(s) source(s) and the vacuum pump). The reactor can beevacuated fully and re-exposed to fresh precursor(s) and/or co-reactantsas many times as necessary. Precursor(s) and/or co-reactants may beintroduced using any mixtures and/or concentrations desired.

Once the SiO₂ surface is passivated the surface comprising SiH is activefor further selective reactions such as, for example, a selective ALDdeposition of SiCN on the Si—H surface. Additional materials that may beselectively deposited on the surface comprising SiH include siliconfilms comprising oxygen, nitrogen, hydrogen and carbon (i.e., SiO_(x),SiN_(x), SiO_(x)N_(y), SiC_(x)N_(y), SiO_(x)C_(y) all possiblyincorporating H as well), metals metal nitrides, and metal oxides.

In some embodiments, a metal oxide film is selectively deposited on thesecond surface. In one example, the metal oxide film may serve as a caplayer on the second surface. The metal oxide film can, for example, bedeposited by atomic layer deposition (ALD), plasma-enhanced ALD (PEALD),chemical vapor deposition (CVD), plasma-enhanced CVD (PECVD), or pulsedCVD. According to one embodiment, the metal oxide film may be selectedfrom the group consisting of HfO₂, ZrO₂, TiO₂, Al₂O₃, and a combinationthereof. In some examples, the metal oxide film may be deposited by ALDusing alternating exposures of a metal organic precursor and an oxidizer(e.g., H₂O, H₂O₂, plasma-excited O₂ or O₃).

Selective depositions according to the present invention can be, forexample, metal and metal oxide layers disclosed in Hamalainen et al.,“Atomic Layer Deposition of Noble Metals and Their Oxides,” Chem. Mater.2014, 26, 786-801; and Johnson et al., “A Brief review of Atomic layerDeposition: From Fundamentals to Applications”, Materials Today, Volume17, Number 5, June 2014, both of which are incorporated herein byreference in their entireties.

In some embodiments, a metal film is selectively deposited on the secondsurface. In one example, the metal film may serve as a cap layer on thesecond surface. In another example, the metal film may serve as aconductive pathway on the second surface (i.e. a line, pad or plug). Inanother example the metal film can, for example, be deposited by atomiclayer deposition (ALD), plasma-enhanced ALD (PEALD), chemical vapordeposition (CVD), plasma-enhanced CVD (PECVD), or pulsed CVD. Accordingto one embodiment, the metal film may be selected from the groupconsisting of Al, Ti, Co, Rh, Ir, Fe, Ru, Os, Mn, Tc, Re, Cu, Ag, Au,Ni, Pd or Pt and a combination thereof.

In some embodiments, a metal or metal nitride film is selectivelydeposited on the second surface. In one example, the metal or metalnitride film may serve as a cap layer on the second surface. In anotherexample, the metal or metal nitride film may serve as a diffusionbarrier layer. The metal or metal nitride film can, for example, bedeposited by atomic layer deposition (ALD), plasma-enhanced ALD (PEALD),chemical vapor deposition (CVD), plasma-enhanced CVD (PECVD), or pulsedCVD. Examples are found in, for example, “IBM Research Report, “AtomicLayer Deposition of Metal and Metal Nitride Thin Films: Current ResearchEfforts and Applications for Semiconductor Device Processing,” RC22737(W0303-012), Mar. 5, 2003.

In some embodiments deposition on a first surface of a substrate asdescribed herein, such as a SiO₂ surface of the substrate, relative to asecond H-terminated surface of the substrate is at least about 90%selective, at least about 95% selective, at least about 96%, 97%, 98% or99% or greater selective. In some embodiments deposition only occurs onthe first surface and does not occur on the second surface. In someembodiments deposition on the first surface of the substrate relative tothe second surface of the substrate is at least about 70% selective, orat least about 80% selective, which may be selective enough for someparticular applications. In some embodiments deposition on the firstsurface of the substrate relative to the second surface of the substrateis at least about 50% selective, which may be selective enough for someparticular applications.

EXAMPLE

The following examples will demonstrate each of the claimed methodsteps. The goal of the invention and that of the experiments that havebeen run is to produce a SiO₂ surface that is nearly free of hydroxylgroups and that, additionally, has a monolayer to sub-monolayer coverageof an organosilane passivating coating. In a preferred embodiment, the‘steric’ hindrance of the passivating molecules on the surface of theSiO₂ closely matches the nearly uniform mean spacing of the surfacehydroxyl groups left after the thermal treatment step has been completed(see illustration of FIG. 2 ).

Step 1: Contacting the Substrate with a Wet Chemical Composition toObtain a Treated Substrate Comprising an Increased Concentration ofSurface Hydroxyl Groups Relative to the Initial Concentration of SurfaceHydroxyl Groups

Example 1: Increase of Surface Hydroxyl Concentration with SC-1 WetChemical Exposure

Independent coupons of SiO₂ and Si(100) are simultaneously processedthrough the following sequence of steps:

Both substrate surfaces were first cleaned in a freshly preparedsolution comprising hydrogen peroxide (28-30%), ammonium hydroxide (28%)and distilled de-ionized water in the ratio of 200 ml:100 ml:1000 ml,the cleaning encompassing first mixing the chemicals together in aquartz beaker, heating the solution in the beaker to 70° C.+/−5° C.,fully immersing the substrate surfaces in the pre-heated cleaningsolution for 10 minutes, removing the substrates from the cleaningsolution and immersing them in a container filled with fresh distilleddeionized water and rinsing said substrates until the cleaning solutionconcentration on the substrates has been diluted to below detectionlimits.

The effectiveness and completeness of the cleaning step can be measuredusing contact angle measurements (goniometer measurements) with theliquid comprised of water or any other suitable fluid. The datapresented herein is for distilled de-ionized water droplets that have avolume of 2 μL.

The starting surfaces (in the as-received state) were measured multipletimes and were found to lie within the ranges shown below:

SiO₂: 32-43°

Si(100): 26-35°

It is believed that the variability observed in the as-received contactangle measurements is the direct result of the adsorption of atmosphericmoisture onto the oxide surfaces that are common to both substrates inthe as-received state.

The surfaces of both the SiO₂ and Si(100) substrates were measured bygoniometer measurements and TOF-SIMS measurements to be hydroxylated toa much higher degree than those of the starting samples. The watercontact angles of the fully hydroxylated surfaces were measured and werefound to lie within the ranges shown below:

SiO₂: 5-10°

Si(100): 5-10°

After the surfaces were demonstrated to be wetting and hydrophilic, thefirst step is complete. Although illustrated through a wet cleaningstep, the invention is not so limited.

The state of the SiO₂ surfaces in the as-received and post-clean statesis also reflected through TOF-SIMS measurements of the SiO₂ substrates.These measurements allow ‘semi-quantitative’ characterization of thesurface concentrations of hydroxyl, hydride and other species present onthe substrates. Representative TOF-SIMS spectra for the as-received andpost-clean states are presented in FIG. 3 , which illustrates a clearincrease in hydroxyl surface concentration post cleaning as shownthrough the difference in the relative intensities between the two SiOHpeaks for the two samples. This increase in hydroxyl surfaceconcentration post cleaning is what enables the desired controlleddecrease in the surface hydroxyl concentration.

Example 2: Conversion of the Si—OH Bonds on the Si(100) Surface to Si—HBonds

The fully hydroxylated SiO₂ and Si(100) surfaces provided by theprevious example are then simultaneously treated using an HF solutionwith a concentration of between 2.0-3.0% (0.1%-5.0% range) for a timesufficient to yield a fully hydrophobic surface on the Si(100) and arethen rinsed in water and blown dry using a stream of ultra-high puritynitrogen. Typically the formation of the Si(100)-H terminated surfacetakes between 80 and 110 s at room temperature (range: 20 s-600 s). Thesurfaces of the SiO₂ and the Si(100) were characterized using contactangle measurements. In general it is believed that the lower the contactangle on the SiO₂ surface and the closer that the contact angle is to90° on the Si(100)-H surface, the better the results of the HF-etch stepfor purposes of the invention. Typical values measured post the HF-etchstep for the two substrate surfaces include:

SiO₂: 4-8°

Si(100): 80°-90°

Due to the high degree of surface hydroxylation, these types of SiO₂substrates are even more susceptible to atmospheric contaminants andmoisture adsorption than the as-received samples, so care should beexercised during their storage and handling prior to loading into thereactor system. For the invention to perform as intended, it isnecessary to fully remove any of this type of excess moisture from thesample surfaces prior to performing the thermal treatment step. This isaccomplished by heating under reduced pressure conditions at atemperature of about 200° C. for a period of 1-10 minutes. Ambient canbe vacuum (or reduced pressure under ultra-high purity inert gas flow(N₂, He, Ne, Ar, etc. . . . ) at a pressure from 10-5 Torr to 740 Torr.

Similarly, the Si(100)-H surface has proven to show limited stabilitytowards air exposure with a propensity to oxidize, thereby negating thechemical differentiation from the SiO₂ surface that is required toachieve selective passivation layer formation. For the invention toperform as intended, it is necessary to load the samples into thereactor system as quickly as possible after the HF-etch to avoidre-oxidation of the surface. Alternatively, the substrates could bestored in a chemically inert environment where the rate of oxidation isvery slow relative to air and then quickly loaded into the reactorsystem.

Although illustrated through a wet clean, any process or combination ofprocesses that can yield a fully hydroxylated SiO₂ surface [α_(OH)(s)=9.5 mole/m²] and a fully hydrogen terminated Si(100) surfacesimultaneously may be used to practice the present invention. Plasmaprocesses (as mentioned previously), wet processes or combinations ofthe two may be used to provide the necessary chemical terminations withthe properties that have been described.

The state of the Si(100) and SiO₂ surfaces in the post-clean states(SC-1 and HF) has also been characterized through TOF-SIMS measurements.These measurements allow semi-quantitative characterization of thesurface concentrations of hydroxyl, hydride and other species present onthe substrates. Representative TOF-SIMS spectra for the Si(100) and SiO₂surfaces post SC-1 clean and HF-etch are shown in FIG. 6 . It isbelieved that the small hydroxyl peak shown in FIG. 6 is due to someoxidation that occurred to the sample in transit for measurement.

Referring to FIG. 6 , despite the oxidation of the Si(100) samples thatis taking place during air exposure, it is clear that the desireddifferentiation in chemical surface terminations has been achievedbetween the SiO₂ and Si(100) surfaces. That is, the SiO₂ surfaces have avery high concentration of hydroxyl groups and the Si(100) surfaces havea very high concentration of hydride groups relative to one another;even with the air oxidation that has occurred on the Si(100) surfaces,it is clear that the two substrates have very different concentrationsof hydroxyl and hydride surface terminations post the cleaning steps. Italso well known to those skilled in the art that an HF etch of singlecrystal silicon surfaces will lead to hydrophobic hydrogen surfaceterminations that are susceptible to oxidation upon prolonged airexposure.

Step 2: Heating the Treated Substrate to a Temperature of from about200° C. to about 600° C., Wherein the Heating Step Converts at Least aPortion of the Surface Hydroxyl Groups on the First Surface to SurfaceSiloxane Groups on the Surface of the Substrate

Example 3: Wet Clean Followed by Thermal Treatment

The purpose of the thermal pre-treatment is to reduce the surfacehydroxyl concentration by the maximal amount, ideally leaving behindonly isolated hydroxyl groups that will then be passivated using one ofthe organosilane precursors using a vapor phase process. To realize themaximal decrease in surface hydroxyl concentration using the thermaltreatment, it is first necessary to produce a fully hydroxylated surface(using wet cleans, vapor phase exposures, plasma treatments, etc. . . .). That is, it is necessary to first increase the surface hydroxylconcentration beyond what is normally observed for an as-received oras-processed silicon dioxide surface prior to the thermal treatment torealize the surface hydroxyl termination of the present invention.

The mechanism behind the thermal treatment reduction of surface hydroxylgroups is a silanol condensation reaction with the elimination of wateraccording to the formula:Si(OH)(surface)+Si(OH)(surface)→Si—O—Si(surface)+H₂O(g)

Three types of samples have been characterized using TOF-SIMS toquantify the surface hydroxyl concentrations in the pre-thermaltreatment and the post-thermal treatment states:

-   -   (1) As-received thermal silicon dioxide “as-received”    -   (2) Silicon dioxide that has been cleaned using (NH₄OH+H₂O₂)        “SC-1”    -   (3) Silicon dioxide that has been cleaned using (NH₄OH+H₂O₂)        “SC-1” followed by an HF-etch “SC-1+HF”

The thermal treatment procedure used for each type of sample wasidentical and involves the following primary steps:

-   -   (1) Preparation of surface hydroxyl coverage (if any) through        appropriate wet chemistry steps    -   (2) Loading of samples into the reactor system where they will        be heated    -   (3) Cycle purging the samples until base pressure for the        reactor system is achieved    -   (4) Purging the reactor system under a flow of ultra-high purity        N₂ for sufficient time to reduce the moisture content in the        reactor system that arises from opening the reactor system and        from the samples themselves    -   (5) Executing the thermal treatment using the pre-programmed        process stored in the furnace temperature controller    -   (6) Cooling the samples to room temperature under a flow of        ultra-high purity N₂    -   (7) Unloading the samples from the reactor system and packaging        them under N₂ for shipment for analysis

Example 4: Thermal Treatment of an SC-1 Cleaned Silicon Dioxide Sample(1,000 Å Thermal SiO₂ on Si(100))

Several 1.5″×1.5″ coupons of a 1,000 Å thermal SiO₂/Si(100) [“1,000 ÅSiO₂”) were cleaved from a 4″ wafer, blown off with a stream of highpurity nitrogen to remove particles and then loaded into a Teflon boatsuitable for immersion in an SC-1 cleaning bath. The boat and sampleswere then immersed in an SC-1 cleaning solution (100 ml ultra-highpurity NH₄OH (28%-30%); 200 ml ultra-high purity H₂O₂ (28-30%); 1000 mldistilled, deionized H₂O) that was pre-heated to a temperature of70+/−5° C. where they were cleaned for 10 minutes. The samples were thenremoved from the cleaning bath and rinsed of chemicals using three dumprinse cycles of distilled, deionized water. The samples were then driedthoroughly using a source of ultra-high purity N₂ gas that was filteredfor particles.

One of the cleaned 1000 Å SiO₂ samples was then loaded into the tube ofa tube furnace reactor system under a flow of 250 sccm ultra-high purityN₂ gas at room temperature. The tube was then sealed and slowlyevacuated to a pressure of 10 mTorr. A flow of 20 sccm N₂ was thenintroduced into the reactor tube and a reduced pressure N₂ purge wasconducted for 2 minutes (at a pressure of 2.3 Torr). The flow of N₂ wasthen stopped and the tube was evacuated to a pressure of ≤5 mTorr. Thepreviously described cycle purging steps are repeated until basepressure is achieved within the reactor system.

After base pressure was achieved, a flow of 20 sccm of ultra-high purityN₂ was introduced into the reactor system and a reduced pressure N₂purge (at 2.3 Torr) was conducted for 1 hour to reduce the backgroundmoisture concentration in the system prior to initiating the thermaltreatment.

The thermal treatment was then performed under a reduced pressure purgeof ultra-high purity N₂ gas (at 2.3 Torr) using the pre-programmedheating process recipe stored on the temperature controller for thefurnace. The heat traces of two independent thermocouples (onerepresenting the external tube temperature—‘wall’ and one representingthe sample temperature—‘sample’) are shown in FIG. 4 , which illustratesthe sample temperature as a function of time.

FIG. 4 also shows the trace of the moisture emission from the samplethat occurs during the thermal treatment step (as measured by an in-situquadrupole mass spectrometer (QMS)). This emission of moisture isconsistent with the silanol condensation reaction described previously.

After the thermal treatment process was completed, the sample was cooledto room temperature under a flow of 20 sccm ultra-high purity N₂ (at apressure of 2.3 Torr). The sample was then unloaded under a flow of 500sccm N₂, quickly enclosed in a container and then stored under N₂ forshipment to the vendor for TOF-SIMS.

Referring now to FIG. 5 , the three types of samples describedpreviously were each processed through the thermal treatment in a manneridentical to that described above for the SC-1 cleaned sample. Each ofthese types of samples were characterized using TOF-SIMS and AFM in thepre-thermal treatment and post-thermal treatment states, as well as bygoniometer measurements (water contact angle measurements). The TOF-SIMSdata for these samples is shown in FIG. 5 . The TOF-SIMS measurementsshow the normalized SiOH+ ion intensities (at mass 45 amu) observed foreach of the samples in the pre-thermal treatment and post-thermaltreatment states. The following key observations are deduced from thisdata set:

1. The as-received sample (which did not have its surface hydroxylconcentration increased beyond its normal state) shows a very smallchange in surface hydroxyl concentration after the thermal treatmentstep. There was no major reduction in surface hydroxyl concentration forthis sample post thermal treatment;

2. Both the SC-1 and the SC-1+HF samples have increased surface hydroxylconcentrations relative to the as-received sample that did not receive astep to increase its surface hydroxyl concentration (as ‘expected’); and

3. Both the SC-1 and the SC-1+HF samples show dramatic decreases insurface hydroxyl concentrations post thermal treatment, toconcentrations well below those measured for the as-received sample postthermal treatment. This important distinction highlights the importanceof the overall process flow to obtain the desired low surface hydroxylconcentration of the present invention. Without first increasing thesurface hydroxyl concentration prior to thermal treatment, no dramaticreduction in the surface hydroxyl concentration is realized through thethermal treatment. This means that most silicon oxide surfaces that areencountered in the industry will not exhibit the behavior desired in thepresent invention, even if they are heated using the thermal treatmentprofile disclosed herein.

Example 5: Thermal Treatment (Reduction of SiO₂ Surface HydroxylConcentration in a Controlled Fashion with Minimal Impact on the HydrideSurface Termination of the Si(100) Surfaces)

The Si(100) and SiO₂ substrates with the desired chemical surfaceterminations prepared by Examples 1 and 2 are next loaded into thereactor system where they are subjected to several pump-purge cycles toremove atmospheric and physisorbed contaminants. The first cycleinvolves pumping the samples to a pressure of between 5 and 10 mTorrabove base pressure, followed by a reduced pressure N₂ purge (10-20 sccmof ultra-high purity N₂) at a pressure of 2-4 Torr for 3 minutes,followed by a pumping step to a pressure of between 1 and 3 mTorr abovebase pressure, followed by a reduced pressure N₂ purge (10-20 sccm ofultra-high purity N₂) at a pressure of 2-4 Torr for 3 minutes, followedby a final pump down step to base pressure. For this experiment, aheated load lock was not available so cycle purging was performed in thereactor tube itself.

The samples were then processed using the thermal treatment to reducethe hydroxyl surface concentration on the SiO₂ surfaces while havingminimal impact on the Si(100) hydride surfaces. The thermal treatmentprofile is shown in FIG. 7 , wherein the x-axis is time in minutes andthe y-axis is temperature in ° C.

The temperatures shown in FIG. 7 are for two independent thermocouples(one embedded within the furnace itself and in contact with the reactortube and one that closely approximates the actual sample temperature).This is the actual profile used to reduce the hydroxyl concentration onthe SiO₂ surfaces through the reaction:Si—OH(s)+Si—OH(s)→Si—O—Si+H₂O(g)

FIG. 8 shows the data collected using the in-situ mass spectrometeroverlaid with the thermal treatment temperature profile and clearlyshows the evolution of water from the samples. The thermal treatment maybe performed over a range of conditions, but at present it has beendemonstrated for reduced pressure operation under a flow of ultra-highpurity N₂ with a pressure of about 2.5 Torr at a flow rate of about 20sccm N₂.

Goniometer measurements of SiO₂ samples post SC-1 clean, post HF-etchand post thermal treatment provide the following water contact anglemeasurements:

SiO₂: 29.1° (for reference: SiO₂+SC-1+thermal treatment=30.5°)

Si(100): 56.3 (showing oxidation upon air exposure; for referenceSi(100)+no thermal treatment dry run sample: 57.9; Si(100) samplesstored in air: show continual oxidation after exposure and storage inair; eventually reach steady state near ˜41.9° which is very close tothe value accepted by those skilled in the art for silicon dioxide).

The state of the Si(100) and SiO₂ surfaces in the post-clean/postthermal treatment states has also been characterized through TOF-SIMSmeasurements. These measurements allow semi-quantitativecharacterization of the surface concentrations of hydroxyl, hydride andother species present on the substrates. Representative TOF-SIMS spectrafor the Si(100) and SiO₂ surfaces post SC-1 clean and HF-etch are shownin FIG. 9 . It is noted that here again oxidation peaks are present inthe Si(100) spectra as a result of air exposure due toequipment/experimental limitations.

Example 6: Thermal Treatment as-Received 1,000 Å SiO₂/Si(100)

Several 1.5″×1.5″ coupons of a 1,000 Å thermal SiO₂/Si(100) (“1,000 ÅSiO₂”) were cleaved from a 4″ wafer, blown off with a stream of highpurity nitrogen to remove particles and then loaded into the tube of atube furnace reactor system under a flow of 250 sccm ultra-high purityN₂ gas at room temperature. The tube was then sealed and slowlyevacuated to a pressure of 10 mTorr. A flow of 20 sccm N₂ was thenintroduced into the reactor tube and a reduced pressure N₂ purge wasconducted for 2 minutes (at a pressure of 2.3 Torr). The flow of N₂ wasthen stopped and the tube was evacuated to a pressure of ≤5 mTorr. Thepreviously described cycle purging steps were repeated until the basepressure of the system was achieved.

After base pressure was achieved, a flow of 20 sccm of ultra-high purityN₂ was introduced into the reactor system and a reduced pressure N₂purge (at 2.3 Torr) was conducted for 1 hour to reduce the backgroundmoisture concentration in the system prior to initiating the thermaltreatment. As known to those skilled in the art, use of a load locksystem will enable greatly reduced cycle times while still providing therequired system purity for the processes described herein to beoperative.

The thermal treatment was then performed under a reduced pressure purgeof ultra-high purity N₂ gas (at 2.3 Torr) using the pre-programmedheating process recipe stored on the temperature controller for thefurnace. The heat traces of two independent thermocouples (onerepresenting the external tube temperature—‘wall’ and one representingthe sample temperature) are shown in FIG. 10 as a function of time.

After the thermal treatment process was completed, the ‘as-received’1,000 Å SiO₂ samples were cooled to room temperature under a flow of 20sccm ultra-high purity N₂ (at a pressure of 2.3 Torr). The samples werethen unloaded under a flow of 500 sccm N₂, quickly enclosed in acontainer and then stored under N₂ for shipment to the vendor foranalytical characterization of their properties.

The ‘as-received’ 1,000 Å SiO₂ samples were characterized using watercontact angle measurements, Atomic Force Microscopy (AFM) andTime-of-Flight Secondary Ion Mass Spectrometry (TOF-SIMS). Forcomparison, ‘as-received’ 1,000 Å SiO₂ samples that did not receive thethermal treatment processing were also characterized in a similarfashion. The results of these analyses are presented in the table below.

Contact Angle Measurements and Surface Roughness Measurements ThermalWater Contact Surface Sample Treatment Angle (Degrees) Roughness (nm)As-Received 1,000 Å No 37.2 0.16 SiO2/Si(100) As-Received 1,000 Å Yes38.8 0.22 SiO2/Si(100)

The TOF-SIMS Spectra of the ‘as-received’ 1,000 Å SiO₂/Si(100) samples,with and without thermal treatment for comparison, are depicted in FIG.11 . Referring to FIG. 11 , some environmental contamination in the formof sodium (Na) and potassium (K) is also visible in the spectrum for the“as-received” 1,000 Å SiO₂/Si(100) post thermal treatment and is likelythe result of sampling handling prior to TOF-SIMS measurements.

Comparison of the two TOF-SIMS spectra of FIG. 11 reveals that thesurface hydroxyl concentrations are largely similar for the two samples.That is, the thermal treatment has not reduced the hydroxylconcentration of the “as-received” 1,000 Å SiO₂/Si(100) sample by asignificant amount.

The quantified data for the normalized SiOH⁺ positive ion, signalintensities (mass 45 amu) and SiH⁺ positive ion, signal intensities(mass 29 amu) representative of the surface concentrations for the twosamples is presented in the table below:

Normalized SiOH⁺ and SiH⁺ intensities for “as-received” 1,000 ÅSiO₂/Si(100) Normalized Normalized Thermal SiOH⁺ SiH⁺ Sample TreatmentIon Intensity Ion Intensity As-Received 1,000 Å No 959 129 SiO2/Si(100)As-Received 1,000 Å Yes 864 181 SiO2/Si(100)

Example 7: Thermal Treatment Example 2 (SC-1 Cleaned Silicon DioxideSample (1,000 Å Thermal SiO₂ on Si(100))

Several 1.5″×1.5″ coupons of a 1,000 Å thermal SiO₂/Si(100) (“1,000 ÅSiO₂”) were cleaved from a 4″ wafer, blown off with a stream of highpurity nitrogen to remove particles and then loaded into a Teflon boatsuitable for immersion in an SC-1 cleaning bath. The boat and sampleswere then immersed in an SC-1 cleaning solution (100 ml ultra-highpurity NH₄OH (28%-30%); 200 ml ultra-high purity H₂O₂ (28-30%); 1000 mldistilled, deionized H₂O) that was pre-heated to a temperature of70+/−5° C. where they were cleaned for 10 minutes. The SC-1 cleaned,1,000 Å SiO₂/Si(100) samples were then removed from the cleaning bathand rinsed of chemicals using three dump rinse cycles of distilled,deionized water. The samples were then dried thoroughly using a sourceof ultra-high purity N₂ gas that was filtered for particles.

Several of the SC-1 cleaned 1000 Å SiO₂ samples were then loaded intothe tube of a tube furnace reactor system under a flow of 250 sccmultra-high purity N₂ gas at room temperature. The tube was then sealedand slowly evacuated to a pressure of 50 mTorr. A flow of 20 sccm N₂ wasthen introduced into the reactor tube and a reduced pressure N₂ purgewas conducted for 2 minutes (at a pressure of 2.3 Torr). The flow of N₂was then stopped and the tube was evacuated to a pressure of ≤5 mTorr.The previously described cycle purging steps were repeated until thebase pressure of the system was achieved.

After base pressure was achieved, a flow of 20 sccm of ultra-high purityN₂ was introduced into the reactor system and a reduced pressure N₂purge (at 2.3 Torr) was conducted for 1 hour to reduce the backgroundmoisture concentration in the system prior to initiating the thermaltreatment. As known to those skilled in the art, use of a load locksystem will enable greatly reduced cycle times while still providing therequired system purity for the processes described herein to beoperative.

The thermal treatment was then performed under a reduced pressure purgeof ultra-high purity N₂ gas (at 2.3 Torr) using the pre-programmedheating process recipe stored on the temperature controller for thefurnace. The heat traces of two independent thermocouples (onerepresenting the external tube temperature—‘wall’ and one representingthe sample temperature) are shown in FIG. 12 .

Overlaid in FIG. 12 is a trace of the moisture emission from the samplethat occurs during the thermal treatment step (as measured by an in-situquadrupole mass spectrometer (QMS)). This emission of moisture isconsistent with the silanol condensation reaction described previously.

After the thermal treatment process was completed, the ‘SC-1 cleaned’1,000 Å SiO₂ samples were cooled to room temperature under a flow of 20sccm ultra-high purity N₂ (at a pressure of 2.3 Torr). The samples werethen unloaded under a flow of 500 sccm N₂, quickly enclosed in acontainer and then stored under N₂ for shipment to the vendor foranalytical characterization of their properties.

The ‘SC-1 cleaned’ 1,000 Å SiO₂ samples were characterized using watercontact angle measurements, Atomic Force Microscopy (AFM) andTime-of-Flight Secondary Ion Mass Spectrometry (TOF-SIMS). Forcomparison, 1,000 Å SiO₂ samples that did not receive the thermaltreatment processing were also characterized in a similar fashion. Theresults of these analyses are presented in the table below.

Contact Angle Measurements and Surface Roughness Measurements ThermalWater contact Surface Sample Treatment Angle (Degrees) Roughness (nm)SC-1 Cleaned 1,000 Å No 8 0.24 SiO2/Si(100) SC-1 Cleaned 1,000 ÅSiO2/Si(100) Yes 26.5 0.39

The TOF-SIMS Spectra of the ‘SC-1 cleaned’ 1,000 Å SiO₂ woo) samples,with and without thermal treatment for comparison, are presented in FIG.13 . It can be seen in FIG. 13 that some environmental contamination inthe form of sodium (Na) and potassium (K) is present in the spectrum forthe “SC-1 cleaned” 1,000 Å SiO₂/Si(100) post thermal treatment and islikely the result of sampling handling prior to TOF-SIMS measurements.

Comparison of the two TOF-SIMS spectra of FIG. 13 reveals that thesurface hydroxyl concentrations are very different between the twosamples. That is, the thermal treatment has greatly reduced the hydroxylconcentration of the “SC-1 cleaned” 1,000 Å SiO₂/Si(100) sample by asignificant amount relative to the sample that was not processed withthe thermal treatment.

The quantified data for the normalized SiOH and SiH surfaceconcentrations for the two samples is presented in the table below:

Normalized SiOH⁺ and SiH⁺ intensities for “SC-1 cleaned” 1,000 ÅSiO₂/Si(100) Normalized Normalized Thermal SiOH⁺ SiH⁺ Sample TreatmentIon Intensity Ion Intensity SC-1 Cleaned 1,000 Å No 1373 159SiO2/Si(100) SC-1 Cleaned 1,000 Å SiO2/Si(100) Yes 258 71.6

Example 8: Thermal Treatment of (‘SC-1 Cleaned, HF-Etched’), 1,000 ÅThermal SiO₂ on Si(100) Sample

Several 1.5″×1.5″ coupons of a 1,000 Å thermal SiO₂/Si(100) [“1,000 ÅSiO₂”) were cleaved from a 4″ wafer, blown off with a stream of highpurity nitrogen to remove particles and then loaded into a Teflon boatsuitable for immersion in an SC-1 cleaning bath. The boat and sampleswere then immersed in an SC-1 cleaning solution (100 ml ultra-highpurity NH₄OH (28%-30%); 200 ml ultra-high purity H₂O₂ (28-30%); 1000 mldistilled, deionized H₂O) that was pre-heated to a temperature of70+/−5° C. where they were cleaned for 10 minutes. The SC-1 cleaned,1,000 Å SiO₂/Si(100) samples were then removed from the cleaning bathand rinsed of chemicals using three dump rinse cycles of distilled,deionized water. The samples were then dried thoroughly using a sourceof ultra-high purity N₂ gas that was filtered for particles.

The dried SC-1 cleaned samples were then placed into a Teflon boatsuitable for immersion in an HF-etch batch. The boat and samples werethen immersed in an HF-etch bath (51 ml ultra-high purity HF (48-49%);1000 ml distilled, deionized H₂O) that was at 21+/−2° C. where they wereetched for 90 seconds. The ‘SC-1 cleaned, HF-etched’, 1,000 ÅSiO₂/Si(100) samples were then removed from the HF solution and quicklyimmersed in distilled, de-ionized water and then dried thoroughly usinga stream of ultra-high purity N₂ gas that was filtered for particles.

Several of the ‘SC-1 cleaned, HF-etched’, 1000 Å SiO₂ samples were thenloaded into the tube of a tube furnace reactor system under a flow of250 sccm ultra-high purity N₂ gas at room temperature with as minimum adelay as possible. The tube was then sealed and slowly evacuated to apressure of 80 mTorr. A flow of 20 sccm N₂ was then introduced into thereactor tube and a reduced pressure N₂ purge was conducted for 2 minutes(at a pressure of 2.3 Torr). The flow of N₂ was then stopped and thetube was evacuated to a pressure of ≤5 mTorr. The previously describedcycle purging steps were repeated until the base pressure of the systemwas achieved.

After base pressure was achieved, a flow of 20 sccm of ultra-high purityN₂ was introduced into the reactor system and a reduced pressure N₂purge (at 2.3 Torr) was conducted for 1 hour to reduce the backgroundmoisture concentration in the system prior to initiating the thermaltreatment. As known to those skilled in the art, use of a load locksystem will enable greatly reduced cycle times while still providing therequired system purity for the processes described herein to beoperative.

The thermal treatment was then performed under a reduced pressure purgeof ultra-high purity N₂ gas (at 2.3 Torr) using the pre-programmedheating process recipe stored on the temperature controller for thefurnace. The heat traces of two independent thermocouples (onerepresenting the external tube temperature—‘wall’ and one representingthe sample temperature) are shown in FIG. 14 .

After the thermal treatment process was completed, the ‘SC-1 cleaned,HF-etched’ 1,000 Å SiO₂ samples were cooled to room temperature under aflow of 20 sccm ultra-high purity N₂ (at a pressure of 2.3 Torr). Thesamples were then unloaded under a flow of 500 sccm N₂, quickly enclosedin a container and then stored under N₂ for shipment to the vendor foranalytical characterization of their properties.

The ‘SC-1 cleaned, HF-etched’ 1,000 Å SiO₂ samples were characterizedusing water contact angle measurements, Atomic Force Microscopy (AFM)and Time-of-Flight Secondary Ion Mass Spectrometry (TOF-SIMS). Forcomparison, ‘SC-1 cleaned, HF-etched’ 1,000 Å SiO₂ samples that did notreceive the thermal treatment processing were also characterized in asimilar fashion. The results of these analyses are presented in thetable below.

Contact Angle Measurements and Surface Roughness Measurements WaterContact Surface Thermal Angle Roughness Sample Treatment (Degrees) (nm)SC-1 Cleaned, HF-etched No 4.6 0.22 1,000 Å SiO2/Si(100) SC-1 Cleaned,HF-etched Yes 39.2 0.25 1,000 Å SiO2/Si(100)

The TOF-SIMS Spectra of the ‘SC-1 cleaned’ 1,000 Å SiO₂/Si(100) samples,with and without thermal treatment for comparison, are shown in FIG. 15. Referring to FIG. 15 , it can be seen that some environmentalcontamination in the form of sodium (Na) and potassium (K) is present inthe spectrum for the “SC-1 cleaned, HF-etched” 1,000 Å SiO₂/Si(100) postthermal treatment and is likely the result of sampling handling prior toTOF-SIMS measurements.

Comparison of the two TOF-SIMS spectra reveals that the surface hydroxylconcentrations are very different between the two samples. That is, thethermal treatment has greatly reduced the hydroxyl concentration of the“SC-1 cleaned” 1,000 Å SiO₂/Si(100) sample by a significant amountrelative to the sample that was not processed with the thermaltreatment. The quantified data for the normalized SiOH and SiH surfaceconcentrations for the two samples is presented in the table below andFIG. 16 .

Normalized SiOH⁺ and SiH⁺ intensities for “SC-1 cleaned” 1,000 ÅSiO₂/Si(100) Thermal Normalized Normalized Treat- SiOH⁺ SiH⁺ Sample mentIon Intensity Ion Intensity SC-1 Cleaned, HF-etched No 2043 76 1,000 ÅSiO2/Si(100) SC-1 Cleaned, HF-etched Yes 501 154 1,000 Å SiO2/Si(100)

The TOF-SIMS measurements show the normalized SiOH⁺ ion intensitiesobserved for each of the samples described in Examples 6-8 in thepre-thermal treatment and post-thermal treatment states. The followingkey observations are deduced from this data set.

First, the as-received sample (which did not have its surface hydroxylconcentration increased beyond its normal state) shows a very smallchange in surface hydroxyl concentration after the thermal treatmentstep. There was no major reduction in surface hydroxyl concentration forthis sample post thermal treatment

Next, both the SC-1 and the SC-1+HF samples have increased surfacehydroxyl concentrations relative to the as-received sample that did notreceive a step to increase its surface hydroxyl concentration.

Finally, both the SC-1 cleaned and the SC-1 cleaned+HF-etched samplesshow dramatic decreases in surface hydroxyl concentrations post thermaltreatment, to concentrations well below those measured for theas-received sample post thermal treatment.

Step 3: Exposing the Substrate, at a Temperature Equal to or Below theHeating Step, to a Silicon-Containing Compound Selected from the GroupConsisting of Formula I and Formula II

Example 9: Selectively Form an Organosilane-Based Passivation Layer onthe SiO₂ Surfaces Provided by the Above Steps, but not on the Si(100)Surfaces

The surfaces provided by the above steps were then processed further toreact the remaining hydroxyl groups on the SiO₂ surfaces withorganosilane precursor molecules using vapor phase reactions, whileavoiding reactions between the hydride groups on the Si(100) surface.The resulting SiO₂ surfaces are thus passivated as fully as possible byeliminating (to a very large degree) the hydroxyl groups that areavailable to serve as reactive nucleation sites during subsequent filmdeposition processes.

The specific molecules tested in these examples include:

ISi(CH₃)₃; BrSi(CH₃)₃; ClSi(CH₃)₃; (CH₃)₂NSi(CH₃)₃

ClSi(CH₂CH₂CH₃)₃

[ClSi(CH₃)₂]₂(CH₂)₂

CH₃)₂NSi(CH₂CH₂CH₃)₃

[ClSi(CH₃)₂]₂(CH₂)₂ and (CH₃)₂NSi(CH₃)₃ (used in combination)

There are many potential vapor phase processes that can be utilized toselectively form passivation layers using molecules of the typedisclosed above. A few specific examples are provided in the followingsection.

Example A: Monopodal Precursor

A mixture of SiO₂ and Si(100) samples that have been processed asdetailed above are disposed in the reactor system at the conclusion ofthermal treatment under a flow of 20 sccm ultra-high purity N₂ at apressure of 2.5 Torr and a temperature of 420° C. While maintaining aflow of ultra-high purity N₂ at reduced pressure, the samples are cooledto 270° C. and equilibrated at that temperature for 10 minutes. The SiO₂samples are then selectively passivated by exposing them to thefollowing reaction sequence:

-   -   (1) The N₂ flow to the system is stopped and the reactor tube        and gas panel are evacuated until the system base pressure is        achieved    -   (2) The gas panel is isolated from the reactor system (static        vacuum conditions) and the lines are charged with vapor phase        (CH₃)₂NSi(CH₃)₃ to the compounds room temperature vapor pressure        of ˜72 Torr, while the tube containing the samples is still        being pumped on.    -   (3) The tube is then isolated from the vacuum pump and the valve        isolating the tube from the vapor phase (CH₃)₂NSi(CH₃)₃ is        opened to introduce (CH₃)₂NSi(CH₃)₃ into the heated tube.    -   (4) The tube is charged with a working pressure of 20 Torr        (comprised of (CH₃)₂NSi(CH₃)₃) at which time the valve to the        bubbler containing the liquid (CH₃)₂NSi(CH₃)₃ and the valve        isolating the gas panel from the tube are both closed.    -   (5) The chemical charge of (CH₃)₂NSi(CH₃)₃ in the heated tube is        reacted with the SiO₂ substrate surfaces for a period of twenty        minutes. During this time, the (CH₃)₂NSi(CH₃)₃ remaining in the        gas panel is removed in preparation for the next chemical dose.    -   (6) After the reaction has been allowed for 20 minutes, a flow        of 20 sccm ultra-high purity N₂ is initiated in the gas panel        and then directed to the reactor system wherein the pressure is        increased to 200 Torr prior to opening the isolation valve and        evacuating the chemical/ultra-high purity N₂ mixture from the        tube under a continuing flow of N₂.    -   (7) The N₂ flow is maintained at a pressure of 2.5 Torr for 1        minute and then terminated. The tube and gas panel are then        evacuated to base pressure (time to evacuate is strongly        dependent upon the precursor being utilized, but typically 1-3        minutes is required).    -   (8) Steps (2)-(7) are then repeated two times to selectively        form a trimethylsilyl surface passivation on the SiO₂ surfaces        while not forming a passivation on the Si(100)-H surface    -   (9) After the three chemical exposure cycles were completed, the        tube and the gas panel were evacuated to base pressure prior to        introducing a flow of ˜20 sccm N₂ through the tube at a pressure        of 2.5 Torr. This condition was maintained while the samples        were cooled to room temperature.

After the samples have cooled to room temperature they are removed fromthe reactor system so that they can be characterized. Representativedata from the experiment described in this Example is presented in FIG.17 , which is comprised of the following data sets:

-   -   (a) Control samples for each of the two experiments (‘dry run’        and ‘live’ run); as-received; post SC-1 clean; post SC-1        clean+HF-etch    -   (b) ‘Dry run’ samples (processed through Steps I-III and then        through the example outlined in steps (1)-(9), but with only        N₂—no (CH₃)₂NSi(CH₃)₃ was introduced during the experiment):        this defines the impact of all of the pre-treatment steps (Steps        I-III) on the starting surfaces (I.e. the hydroxyl surface        terminations on the SiO₂ surface and the hydride surface        termination on the Si(100) surface)

‘Live run’ samples (processed through the above steps and then runthrough the example outlined in steps (1)-(9) of Example A.

Referring to FIG. 17 , the measurements of the control samples from bothexperiments are very similar and reflect the high degree ofrepeatability of the cleaning processes that were developed. The mostimportant data set is that of the live run samples. They exhibitproperties that are very much in agreement with the conclusion thattrimethylsilyl surface passivation has been selectively formed on theSiO₂ surfaces, but not on the Si(100) surfaces. Namely, the SiO₂surfaces exhibit high water contact angles (approaching 100°) afterprocessing, suggestive that the desired passivation layer has beenformed on the SiO₂ surfaces, while the Si(100) surfaces exhibitsignificantly reduced water contact angles (suggestive that nopassivation layer has been formed on the Si(100) surfaces).

The decrease in the Si(100) contact angle is related to the airoxidation of the Si(100) sample surfaces upon their removal from thereactor system. This has been proven by tracking the water contact angleof the Si(100) samples from both the dry and live runs as a function oftime, as well as by generating data related to samples that were cleanedand etched but never put in the reactor system (i.e. allowed to stand inair post the HF-etch step). In all cases, the contact angle continues todecrease until it approaches ˜41.9°, the value accepted by those skilledin the art for the water contact angle of silicon dioxide. Furthermore,Si(100) samples that do not receive an HF-etch exhibit water contactangles >96°, very similar to the SiO₂ surfaces (as would be expected byone skilled in the art since they will be hydroxylated SiO₂ surfaces inthe absence of the HF-etch step). This behavior is consistent with thelack of formation of any trimethylsilyl surface passivation on theSi(100) surfaces.

Example B: Bipodal Precursor

A mixture of SiO₂ and Si(100) samples that have been processed throughthe steps detailed above are disposed in the reactor system at theconclusion of the thermal treatment step under a flow of 20 sccmultra-high purity N₂ at a pressure of 2.5 Torr and a temperature of 420°C. While maintaining a flow of ultra-high purity N₂ at reduced pressure,the samples are cooled to 405° C. and equilibrated at that temperaturefor 10 minutes. The SiO₂ samples are then selectively passivated byexposing them to the following reaction sequence:

-   -   (1) The N₂ flow to the system is stopped and the reactor tube        and gas panel are evacuated until the system base pressure is        achieved    -   (2) The gas panel is isolated from the reactor system (static        vacuum conditions) and the lines are charged with vapor phase        [ClSi(CH₃)₂]₂(CH₂)₂ to the compounds room temperature vapor        pressure of 0.4 Torr, while the tube containing the samples is        still being pumped on.    -   (3) The tube is then isolated from the vacuum pump and the valve        isolating the tube from the vapor phase [ClSi(CH₃)₂]₂(CH₂)₂ is        opened to begin allowing [ClSi(CH₃)₂]₂(CH₂)₂ into the heated        tube.    -   (4) The tube is charged with a working pressure of 0.200 to        0.245 Torr (comprised of [ClSi(CH₃)₂]₂(CH₂)₂) at which time the        valve to the bubbler containing the liquid [ClSi(CH₃)₂]₂(CH₂)₂        and the valve isolating the gas panel from the tube are both        closed.    -   (5) The chemical charge of [ClSi(CH₃)₂]₂(CH₂)₂ in the heated        tube is reacted with the SiO₂ substrate surfaces for a period of        twenty minutes. During this time, the [ClSi(CH₃)₂]₂(CH₂)₂        remaining in the gas panel is evacuated using the vacuum bypass        manifold in preparation for the next chemical dose.    -   (6) After the reaction has been allowed for 10 minutes, a flow        of 20 sccm ultra-high purity N₂ is initiated in the gas panel        and then directed to the reactor system wherein the pressure is        increased to 200 Torr prior to opening the isolation valve and        evacuating the chemical/ultra-high purity N₂ mixture from the        tube under a continuing flow of N₂.    -   (7) The N₂ flow is maintained at a pressure of 2.5 Torr for 1        minute and then terminated. The tube and gas panel are then        evacuated to base pressure (time to evacuate is strongly        dependent upon the precursor being utilized, but typically 1-3        minutes is required).    -   (8) Steps (2)-(7) are then repeated nine times to selectively        form a bis-dimethylsilylethane surface passivation on the SiO₂        surfaces while not forming a passivation on the Si(100)-H        surface.    -   (9) After the desired number of cycles have been completed, the        tube and the gas panel are evacuated to base pressure, then a        flow of ˜20 sccm N₂ is directed through the gas panel to the        tube at a pressure of 2.5 Torr and is maintained as the tube        containing the samples is cooled to room temperature

After the samples have cooled to room temperature they are removed fromthe reactor system so that they can be characterized. Representativedata from the experiment just described is presented in FIG. 18 . It iscomprised of the following data sets:

-   -   (a) Control samples for each of the two experiments (‘dry run’        and ‘live’ run); as-received; post SC-1 clean; post SC-1        clean+HF-etch    -   (b) ‘Live run’ samples (processed through Steps I-III and then        run through the example outlined in steps (1)-(9) of Example B

The data presented for this example and shown in FIG. 18 is quitesimilar to that shared for Example 1 in that the measurements from thecontrol samples are nearly identical to those shared for Example A, thatthe Si(100) Live Run samples exhibit nearly identical contact angles tothose observed for the Si(100) samples in Example A (suggestive of airoxidation in this case, once again) and that there is a large andpositive change in contact angle for the SiO₂ samples after exposure tothe passivation precursor.

Example 10: Selective Formation of Trimethylsilyl Surface Passivation on‘SC-1 Cleaned, HF-etched’, 1,000 Å SiO₂/Si(100) and Not on Si(100) Using(CH₃)₂NSi(CH₃)₃ (Dimethylaminotrimethylsilane) at 270° C. with ThermalTreatment Processing

Several 1.5″×1.5″ coupons of a 1,000 Å thermal SiO₂/Si(100) [“1,000 ÅSiO₂”) and Si(100) were cleaved from 4″ wafers, blown off with a streamof high purity nitrogen to remove particles and then loaded into aTeflon boat suitable for immersion in an SC-1 cleaning bath. The boatand samples were then immersed in an SC-1 cleaning solution (100 mlultra-high purity NH₄OH (28%-30%); 200 ml ultra-high purity H₂O₂(28-30%); 1000 ml distilled, deionized H₂O) that was pre-heated to atemperature of 70+/−5° C. where they were cleaned for 10 minutes. TheSC-1 cleaned, 1,000 Å SiO₂/(100) and Si(100) samples were then removedfrom the cleaning bath and rinsed of chemicals using three dump rinsecycles of distilled, deionized water. The samples were then driedthoroughly using a source of ultra-high purity N₂ gas that was filteredfor particles.

The dried SC-1 cleaned samples were then placed into a Teflon boatsuitable for immersion in an HF-etch batch. The boat and samples werethen immersed in an HF-etch bath (51 ml ultra-high purity HF (48-49%);1000 ml distilled, deionized H₂O) that was at 21+/−2° C. where they wereetched for 90 seconds. The ‘SC-1 cleaned, HF-etched’, 1,000 ÅSiO₂/Si(100) and Si(100) samples were then removed from the HF solutionand quickly immersed in distilled, de-ionized water and then driedthoroughly using a source of ultra-high purity N₂ gas that was filteredfor particles.

Several of the ‘SC-1 cleaned, HF-etched’, 1000 Å SiO₂ and Si(100)samples were then loaded into the tube of a tube furnace reactor systemunder a flow of 250 sccm ultra-high purity N₂ gas at room temperaturewith as minimum a delay as possible. The tube was then sealed and slowlyevacuated to a pressure of 80 mTorr. A flow of 20 sccm N₂ was thenintroduced into the reactor tube and a reduced pressure N₂ purge wasconducted for 2 minutes (at a pressure of 2.3 Torr). The flow of N₂ wasthen stopped and the tube was evacuated to a pressure of ≤5 mTorr. Thepreviously described cycle purging steps were repeated until the basepressure of the system was achieved.

After base pressure was achieved, a flow of 20 sccm of ultra-high purityN₂ was introduced into the reactor system and a reduced pressure N₂purge (at 2.3 Torr) was conducted for 1 hour to reduce the backgroundmoisture concentration in the system prior to initiating the thermaltreatment. As known to those skilled in the art, use of a load locksystem will enable greatly reduced cycle times while still providing therequired system purity for the processes described herein to beoperative.

The thermal treatment was then performed under a reduced pressure purgeof ultra-high purity N₂ gas (at 2.3 Torr) using the pre-programmedheating process recipe stored on the temperature controller for thefurnace. The heat traces of two independent thermocouples (onerepresenting the external tube temperature—‘wall’ and one representingthe sample temperature) are shown in FIG. 19 .

After the thermal treatment was completed, a flow of 20 sccm ultra-highpurity N₂ was maintained through the tube at a pressure of 2.5 Torrwhile the sample temperature was reduced to 270° C. The samples wereequilibrated at 270° C. for 10 minutes, the N₂ flow was terminated andthe tube was fully evacuated to a pressure of about 1 mTorr. The tubewas then charged with a first chemical dose ofdimethylaminotrimethylsilane [(CH₃)₂NSi(CH₃)₃] to a pressure of 19.9Torr and then isolated at this pressure for 20 minutes. The firstchemical dose was then removed from the chamber using a combination ofreduced pressure N₂ purging and evacuation that encompassed firstintroducing a dynamic flow of 20 sccm N₂ at a pressure of 2.5 Torr forone minute, followed by evacuation of the tube to a pressure not greaterthan 10 mTorr for two minutes. The second chemical dose of(CH₃)₂NSi(CH₃)₃ was then introduced in a manner identical to the firstdose except that the pressure of the second dose was 20.8 Torr. Thesecond dose was then removed in the same manner as the first chemicaldose prior to the introduction of the third chemical dose. The thirdchemical dose of (CH₃)₂NSi(CH₃)₃ was then introduced in a manneridentical to the first and second doses except that the pressure of thethird dose was 20.5 Torr. The third chemical dose was then removed inthe same manner as the first and second chemical doses, completing theselective formation of the trimethylsilyl surface passivation on the‘SC-1 cleaned, HF-etched’, 1,000 Å SiO₂ samples, but not on the Si(100)samples.

After the selective passivation formation was completed, the ‘SC-1cleaned, HF-etched’ 1,000 Å SiO₂ and Si(100) samples were cooled to roomtemperature under a flow of 20 sccm ultra-high purity N₂ at a pressureof 2.3 Torr. The samples were then unloaded under a flow of 500 sccm N₂,quickly enclosed in a container and then stored under N₂ for shipment tothe vendor for analytical characterization of their properties.

The ‘SC-1 cleaned, HF-etched’ 1,000 Å SiO₂ and Si(100) samples werecharacterized using water contact angle measurements, Atomic ForceMicroscopy (AFM) and Time-of-Flight Secondary Ion Mass Spectrometry(TOF-SIMS). For comparison, ‘SC-1 cleaned, HF-etched’ 1,000 Å SiO₂samples that did not receive the thermal treatment processing were alsocharacterized in a similar fashion. The results of these analyses arepresented in the tables below:

Contact Angle Measurements and Surface Roughness Measurements WaterThermal Contact Surface Treat- Angle Roughness Sample ment (Degrees)(nm) SC-1 Cleaned, HF-etched Yes 96.8 0.23 1,000 Å SiO2/Si(100) SC-1Cleaned, HF-etched Yes 45.6 0.18 Si(100)

The samples were also analyzed by X-Ray Photoelectron Spectroscopy (XPS)and the results are presented in the table below:

Carbon Oxygen Silicon O/Si Sample (atomic %) (atomic %) (atomic %) RatioSC-1 Cleaned, HF-etched 3.7 65.2 30.8 2.11 1,000 Å SiO2/Si(100) SC-1Cleaned, HF-etched 7.7 25.2 66.7 0.38 Si(100)

The TOF-SIMS spectra for the ‘SC-1 cleaned, HF-etched’ 1,000 Å SiO₂ andSi(100) samples are presented in FIG. 20 . The lack of observation ofthe peaks associated with trimethylsilyl surface passivation in theSi(100) TOF-SIMS spectrum in FIG. 20 is evidence that the formation ofthe passivation layer was limited to the ‘SC-1 cleaned, HF-etched’ 1,000Å SiO₂/Si(100) substrate. That is, the passivation was formedselectively on the desired surface and not on the Si(100) surface. Thisconclusion is also supported by the water contact angle measurements forthe samples and the AFM surface roughness measurements for the samples.

Normalized Ion Intensities for positive ions with mass 45 amu, 29 amu,43 amu, 59 amu and 73 amu for “SC-1 cleaned, HF-etched” 1,000 ÅSiO₂/Si(100) and Si(100) are shown in the table below.

Thermal Sample Treatment mass 45 amu mass 29 amu mass 43 amu mass 59 amumass 73 amu SC-1 cleaned, HF-etched Yes 477 466 1223 118 1187 1,000 ÅSiO2/Si(100) SC-1 cleaned, HF-etched Yes 1690 1213 99 5 10 Si(100)

The observation of trace signals for some of the ions associated withtrimethylsilyl surface passivation on the Si(100) sample is consistentwith the levels observed on the control samples (for which nodimethylaminotrimethylsilane was introduced into the reactor system) ascan be observed in the table below.

Thermal Sample Treatment mass 45 amu mass 29 amu mass 43 amu mass 59 amumass 73 amu SC-1 Cleaned, HF-etched Yes 501 154 211 6.91 22.1 1,000 ÅSiO2/Si(100) SC-1 Cleaned, HF-etched Yes 1327 1073 113 4.6 1.2 Si(100)

Example 11 (Comparative): Selective Formation of Trimethylsilyl SurfacePassivation on ‘SC-1 Cleaned, HF-Etched’, 1,000 Å SiO₂/Si(100) and noton Si(100) Using (CH₃)₂NSi(CH₃)₃ (Dimethylaminotrimethylsilane) at 270°C. without Thermal Treatment Processing

Several 1.5″×1.5″ coupons of a 1,000 Å thermal SiO₂/Si(100) [“1,000 ÅSiO₂”) and Si(100) were cleaved from 4″ wafers, blown off with a streamof high purity nitrogen to remove particles and then loaded into aTeflon boat suitable for immersion in an SC-1 cleaning bath. The boatand samples were then immersed in an SC-1 cleaning solution (100 mlultra-high purity NH₄OH (28%-30%); 200 nil ultra-high purity H₂O₂(28-30%); 1000 ml distilled, deionized H₂O) that was pre-heated to atemperature of 70+/−5° C. where they were cleaned for 10 minutes. TheSC-1 cleaned, 1,000 Å SiO₂/(100) and Si(100) samples were then removedfrom the cleaning bath and rinsed of chemicals using three dump rinsecycles of distilled, deionized water. The samples were then driedthoroughly using a source of ultra-high purity N₂ gas that was filteredfor particles.

The dried SC-1 cleaned samples were then placed into a Teflon boatsuitable for immersion in an HF-etch batch. The boat and samples werethen immersed in an HF-etch bath (51 ml ultra-high purity HF (48-49%);1000 nil distilled, deionized H₂O) that was at 21+/−2° C. where theywere etched for 90 seconds. The ‘SC-1 cleaned, HF-etched’, 1,000 ÅSiO₂/Si(100) and Si(100) samples were then removed from the HF solutionand quickly immersed in distilled, de-ionized water and then driedthoroughly using a source of ultra-high purity N₂ gas that was filteredfor particles.

Several of the ‘SC-1 cleaned, HF-etched’, 1000 Å SiO₂ and Si(100)samples were then loaded into the tube of a tube furnace reactor systemunder a flow of 250 sccm ultra-high purity N₂ gas at room temperaturewith as minimum a delay as possible. The tube was then sealed and slowlyevacuated to a pressure of 80 mTorr. A flow of 20 sccm N₂ was thenintroduced into the reactor tube and a reduced pressure N₂ purge wasconducted for 2 minutes (at a pressure of 2.3 Torr). The flow of N₂ wasthen stopped and the tube was evacuated to a pressure of ≤5 mTorr. Thepreviously described cycle purging steps were repeated until the basepressure of the system was achieved.

After base pressure was achieved, a flow of 20 sccm of ultra-high purityN₂ was introduced into the reactor system and a reduced pressure N₂purge (at 2.3 Torr) was conducted for 1 hour to reduce the backgroundmoisture concentration in the system prior to initiating the thermaltreatment. As known to those skilled in the art, use of a load locksystem will enable greatly reduced cycle times while still providing therequired system purity for the processes described herein to beoperative.

The samples were equilibrated at 270° C. for 10 minutes, the N₂ flow wasterminated and the tube was fully evacuated to a pressure of no morethan 1 mTorr. The tube was then charged with a first chemical dose ofdimethylaminotrimethylsilane [(CH₃)₂NSi(CH₃)₃] to a pressure of 20.8Torr and then isolated at this pressure for 20 minutes. The firstchemical dose was then removed from the chamber using a combination ofreduced pressure N₂ purging and evacuation that encompassed firstintroducing a dynamic flow of 20 sccm N₂ at a pressure of 2.5 Torr forone minute, followed by evacuation of the tube to a pressure not greaterthan 10 mTorr for two minutes. The second chemical dose of(CH₃)₂NSi(CH₃)₃ was then introduced in a manner identical to the firstdose except that the pressure of the second dose was 21.0 Torr. Thesecond dose was then removed in the same manner as the first chemicaldose prior to the introduction of the third chemical dose. The thirdchemical dose of (CH₃)₂NSi(CH₃)₃ was then introduced in a manneridentical to the first and second doses except that the pressure of thethird dose was 21.4 Torr. The third chemical dose was then removed inthe same manner as the first and second chemical doses, completing theselective formation of the trimethylsilyl surface passivation on the‘SC-1 cleaned, HF-etched’, 1,000 Å SiO₂ samples, but not on the Si(100)samples.

After the selective passivation formation was completed, the ‘SC-1cleaned, HF-etched’ 1,000 Å SiO₂ and Si(100) samples were cooled to roomtemperature under a flow of 20 sccm ultra-high purity N₂ at a pressureof 2.3 Torr. The samples were then unloaded under a flow of 500 sccm N₂,quickly enclosed in a container and then stored under N₂ for shipment tothe vendor for analytical characterization of their properties.

The ‘SC-1 cleaned, HF-etched’ 1,000 Å SiO₂ and Si(100) samples werecharacterized using water contact angle measurements, Atomic ForceMicroscopy (AFM) and Time-of-Flight Secondary Ion Mass Spectrometry(TOF-SIMS). For comparison, ‘SC-1 cleaned, HF-etched’ 1,000 Å SiO₂samples that did not receive the thermal treatment processing were alsocharacterized in a similar fashion. The results of these analyses arepresented in the tables below:

Contact Angle Measurements and Surface Roughness Measurements WaterThermal Contact Surface Treat- Angle Roughness Sample ment (Degrees)(nm) SC-1 Cleaned, HF-etched No 101 0.27 1,000 Å SiO2/Si(100) SC-1Cleaned, HF-etched No 54 0.2 Si(100)

The samples were also analyzed by X-Ray Photoelectron Spectroscopy (XPS)and the results are presented in the table below.

Carbon Oxygen Silicon O/ Sample (atomic %) (atomic %) (atomic %) SiRatio SC-1 Cleaned, HF-etched 2.5 66.2 31.2 2.12 1,000 Å SiO2/Si(100)SC-1 Cleaned, HF-etched 6 27.7 65.9 0.42 Si(100)

The TOF-SIMS spectra for the ‘SC-1 cleaned, HF-etched’ 1,000 Å SiO₂ andSi(100) samples are presented in FIG. 21 . Referring to FIG. 21 , thelack of observation of the peaks associated with trimethylsilyl surfacepassivation in the Si(100) TOF-SIMS spectrum is evidence that theformation of the passivation layer was limited to the ‘SC-1 cleaned,HF-etched’ 1,000 Å SiO₂/Si(100) substrate. That is, the passivation wasformed selectively on the desired surface and not on the Si(100)surface. Comparison with the samples of example 1 reveals that theresidual hydroxyl concentration on the surface of the sample that didnot receive the thermal treatment is markedly higher than that of thesample that did receive the thermal treatment in accordance with theteachings of the present invention.

Normalized Ion Intensities for positive ions with mass 45 amu, 29 amu,43 amu, 59 amu and 73 amu for “SC-1 cleaned, HF-etched” 1,000 ÅSiO₂/Si(100) and Si(100) are “shown in the table below.

Thermal Sample Treatment mass 45 amu mass 29 amu mass 43 amu mass 59 amumass 73 amu SC-1 Cleaned, HF-etched No 672 493 1433 149 1477 1,000 ÅSiO2/Si(100) SC-1 Cleaned, HF-etched No 863 1803 121 98 24.5 Si(100)

Example 12: Selective Formation of Bis-Dimethylsilylethane SurfacePassivation on ‘SC-1 Cleaned, HF-Etched’, 1,000 Å SiO₂/Si(100) and noton Si(100) Using [Cl(CH₃)₂Si]₂(CH₂)₂ (1,2-bis-chlorodimethylsilylethane)at 370° C. with Thermal Treatment Processing

Several 1.5″×1.5″ coupons of a 1,000 Å thermal SiO₂/Si(100) [“1,000 ÅSiO₂”) and Si(100) were cleaved from 4″ wafers, blown off with a streamof high purity nitrogen to remove particles and then loaded into aTeflon boat suitable for immersion in an SC-1 cleaning bath. The boatand samples were then immersed in an SC-1 cleaning solution (100 mlultra-high purity NH₄OH (28%-30%); 200 ml ultra-high purity H₂O₂(28-30%); 1000 ml distilled, deionized H₂O) that was pre-heated to atemperature of 70+/−5° C. where they were cleaned for 10 minutes. TheSC-1 cleaned, 1,000 Å SiO₂/Si(100) and Si(100) samples were then removedfrom the cleaning bath and rinsed of chemicals using three dump rinsecycles of distilled, deionized water. The samples were then driedthoroughly using a source of ultra-high purity N₂ gas that was filteredfor particles.

The dried SC-1 cleaned samples were then placed into a Teflon boatsuitable for immersion in an HF-etch batch. The boat and samples werethen immersed in an HF-etch bath (51 ml ultra-high purity HF (48-49%);1000 ml distilled, deionized H₂O) that was at 21+/−2° C. where they wereetched for 90 seconds. The ‘SC-1 cleaned, HF-etched’, 1,000 ÅSiO₂/Si(100) and Si(100) samples were then removed from the HF solutionand quickly immersed in distilled, de-ionized water and then driedthoroughly using a source of ultra-high purity N₂ gas that was filteredfor particles.

Several of the ‘SC-1 cleaned, HF-etched’, 1000 Å SiO₂ and Si(100)samples were then loaded into the tube of a tube furnace reactor systemunder a flow of 250 sccm ultra-high purity N₂ gas at room temperaturewith as minimum a delay as possible. The tube was then sealed and slowlyevacuated to a pressure of 80 mTorr. A flow of 20 sccm N₂ was thenintroduced into the reactor tube and a reduced pressure N₂ purge wasconducted for 2 minutes (at a pressure of 2.3 Torr). The flow of N₂ wasthen stopped and the tube was evacuated to a pressure of ≤5 mTorr. Thepreviously described cycle purging steps were repeated until the basepressure of the system was achieved.

After base pressure was achieved, a flow of 20 sccm of ultra-high purityN₂ was introduced into the reactor system and a reduced pressure N₂purge (at 2.3 Torr) was conducted for 1 hour to reduce the backgroundmoisture concentration in the system prior to initiating the thermaltreatment. As known to those skilled in the art, use of a load locksystem will enable greatly reduced cycle times while still providing therequired system purity for the processes described herein to beoperative.

The thermal treatment was then performed under a reduced pressure purgeof ultra-high purity N₂ gas (at 2.3 Torr) using the pre-programmedheating process recipe stored on the temperature controller for thefurnace. The heat traces of two independent thermocouples (onerepresenting the external tube temperature—‘wall’ and one representingthe sample temperature) are shown in FIG. 22 .

After the thermal treatment was completed, a flow of 20 sccm ultra-highpurity N₂ was maintained through the tube at a pressure of 2.5 Torrwhile the sample temperature was reduced to 370° C. The samples wereequilibrated at 370° C. for 10 minutes, the N₂ flow was terminated andthe tube was fully evacuated to a pressure of no more than 1 mTorr. Thetube was then charged with a first chemical dose of1,2-bis-chlorodimethylsilylethane [(Cl(CH₃)₂Si]₂(CH₂)₂] to a pressure of0.24 Torr and then isolated at this pressure for 10 minutes. The firstchemical dose was then removed from the chamber using a combination ofreduced pressure N₂ purging and evacuation that encompassed firstintroducing a dynamic flow of 20 sccm N₂ at a pressure of 2.5 Torr forone minute, followed by evacuation of the tube to a pressure not greaterthan 10 mTorr for two minutes. The second chemical dose of(Cl(CH₃)₂Si]₂(CH₂)₂ was then introduced in a manner identical to thefirst dose except that the pressure of the second dose was 0.25 Torr.The second dose was then removed in the same manner as the firstchemical dose prior to the introduction of the third chemical dose. Thethird through twelfth chemical doses of (Cl(CH₃)₂Si]₂(CH₂)₂ were thenintroduced in a manner identical to the first and second doses exceptthat the pressure of these doses varied slightly between 0.24 Torr and0.26 Torr. The third through twelfth doses were then removed in the samemanner as the first and second chemical doses, completing the selectiveformation of the bis-dimethylsilylethane surface passivation on the‘SC-1 cleaned, HF-etched’, 1,000 Å SiO₂ samples, but not on the Si(100)samples.

After the selective passivation formation was completed, the ‘SC-1cleaned, HF-etched’ 1,000 Å SiO₂ and Si(100) samples were cooled to roomtemperature under a flow of 20 sccm ultra-high purity N₂ at a pressureof 2.3 Torr. The samples were then unloaded under a flow of 500 sccm N₂,quickly enclosed in a container and then stored under N₂ for shipment tothe vendor for analytical characterization of their properties.

The ‘SC-1 cleaned, HF-etched’ 1,000 Å SiO₂ and Si(100) samples werecharacterized using water contact angle measurements, Atomic ForceMicroscopy (AFM) and Time-of-Flight Secondary Ion Mass Spectrometry(TOF-SIMS). The results of these analyses are presented in the tablesbelow:

Contact Angle Measurements and Surface Roughness Measurements WaterThermal Contact Surface Treat- Angle Roughness Sample ment (Degrees)(nm) SC-1 Cleaned, HF-etched Yes 85.9 0.28 1,000 Å SiO2/Si(100) SC-1Cleaned, HF-etched Yes 56.4 0.18 Si(100)

The samples were also analyzed by X-Ray Photoelectron Spectroscopy (XPS)and the results are presented in the table below:

Carbon Oxygen Silicon O/ Sample (atomic %) (atomic %) (atomic %) SiRatio SC-1 Cleaned, HF-etched 2 66.3 31.7 2.09 1,000 Å SiO2/Si(100) SC-1Cleaned, HF-etched 5 28.6 65.7 0.44 Si(100)

The TOF-SIMS spectra for the ‘SC-1 cleaned, HF-etched’ 1,000 Å SiO₂ andSi(100) samples are presented in FIG. 23 . Referring to FIG. 23 , thelack of observation of the peaks associated with bis-dimethylsilylethanesurface passivation in the Si(100) TOF-SIMS spectrum is evidence thatthe formation of the passivation layer was limited to the ‘SC-1 cleaned,HF-etched’ 1,000 Å SiO₂/Si(100) substrate. That is, the passivation wasformed selectively on the desired surface and not on the Si(100)surface.

Normalized Ion Intensities for positive ions with mass 45 amu, 29 amu,43 amu, 59 amu and 73 amu for“SC-1 cleaned, HF-etched” 1,000 ÅSiO₂/Si(100) and Si(100) are shown in the table below.

Thermal Sample Treatment mass 45 amu mass 29 amu mass 43 amu mass 59 amumass 73 amu SC-1 Cleaned, HF-etched Yes 745 292 757 283 126 1000 ÅSiO2/Si(100) SC-1 Cleaned, HF-etched Yes 1200 1527 63 2.2 0.4 Si(100)

Example 13 (Comparative): Selective Formation of Bis-DimethylsilylethaneSurface Passivation on ‘SC-1 Cleaned, HF-Etched’, 1,000 Å SiO₂/Si(100)and not on Si(100) Using [Cl(CH₃)₂Si]₂(CH₂)₂(1,2-bis-chlorodimethylsilylethane) at 370° C. without Thermal TreatmentProcessing

Several 1.5″×1.5″ coupons of a 1,000 Å thermal SiO₂/Si(100) [“1,000 ÅSiO₂”) and Si(100) were cleaved from 4″ wafers, blown off with a streamof high purity nitrogen to remove particles and then loaded into aTeflon boat suitable for immersion in an SC-1 cleaning bath. The boatand samples were then immersed in an SC-1 cleaning solution (100 mlultra-high purity NH₄OH (28%-30%); 200 ml ultra-high purity H₂O₂(28-30%); 1000 nil distilled, deionized H₂O) that was pre-heated to atemperature of 70+/−5° C. where they were cleaned for 10 minutes. TheSC-1 cleaned, 1,000 Å SiO₂/(100) and Si(100) samples were then removedfrom the cleaning bath and rinsed of chemicals using three dump rinsecycles of distilled, deionized water. The samples were then driedthoroughly using a source of ultra-high purity N₂ gas that was filteredfor particles.

The dried SC-1 cleaned samples were then placed into a Teflon boatsuitable for immersion in an HF-etch batch. The boat and samples werethen immersed in an HF-etch bath (51 ml ultra-high purity HF (48-49%);1000 ml distilled, deionized H₂O) that was at 21+/−2° C. where they wereetched for 90 seconds. The ‘SC-1 cleaned, HF-etched’, 1,000 ÅSiO₂/Si(100) and Si(100) samples were then removed from the HF solutionand quickly immersed in distilled, de-ionized water and then driedthoroughly using a source of ultra-high purity N₂ gas that was filteredfor particles.

Several of the ‘SC-1 cleaned, HF-etched’, 1000 Å SiO₂ and Si(100)samples were then loaded into the tube of a tube furnace reactor systemunder a flow of 250 sccm ultra-high purity N₂ gas at room temperaturewith as minimum a delay as possible. The tube was then sealed and slowlyevacuated to a pressure of 80 mTorr. A flow of 20 sccm N₂ was thenintroduced into the reactor tube and a reduced pressure N₂ purge wasconducted for 2 minutes (at a pressure of 2.3 Torr). The flow of N₂ wasthen stopped and the tube was evacuated to a pressure of ≤5 mTorr. Thepreviously described cycle purging steps were repeated until the basepressure of the system was achieved.

After base pressure was achieved, a flow of 20 sccm of ultra-high purityN₂ was introduced into the reactor system and a reduced pressure N₂purge (at 2.3 Torr) was conducted for 1 hour to reduce the backgroundmoisture concentration in the system prior to initiating the thermaltreatment. As known to those skilled in the art, use of a load locksystem will enable greatly reduced cycle times while still providing therequired system purity for the processes described herein to beoperative.

The samples were equilibrated at 370° C. for 10 minutes, the N₂ flow wasterminated and the tube was fully evacuated to a pressure of no morethan 1 mTorr. The tube was then charged with a first chemical dose of1,2-bis-chlorodimethylsilylethane [(Cl(CH₃)₂Si]₂(CH₂)₂] to a pressure of0.24 Torr and then isolated at this pressure for 10 minutes. The firstchemical dose was then removed from the chamber using a combination ofreduced pressure N₂ purging and evacuation that encompassed firstintroducing a dynamic flow of 20 sccm N₂ at a pressure of 2.5 Torr forone minute, followed by evacuation of the tube to a pressure not greaterthan 10 mTorr for two minutes. The second chemical dose of(Cl(CH₃)₂Si]₂(CH₂)₂ was then introduced in a manner identical to thefirst dose except that the pressure of the second dose was 0.23 Torr.The second dose was then removed in the same manner as the firstchemical dose prior to the introduction of the third chemical dose. Thethird through twelfth chemical doses of (Cl(CH₃)₂Si]₂(CH₂)₂ were thenintroduced in a manner identical to the first and second doses exceptthat the pressure of these doses varied slightly between 0.23 Torr and0.25 Torr. The third through twelfth doses were then removed in the samemanner as the first and second chemical doses, completing the selectiveformation of the bis-dimethylsilylethane surface passivation on the‘SC-1 cleaned, HF-etched’, 1,000 Å SiO₂ samples, but not on the Si(100)samples.

After the selective passivation formation was completed, the ‘SC-1cleaned, HF-etched’ 1,000 Å SiO₂ and Si(100) samples were cooled to roomtemperature under a flow of 20 sccm ultra-high purity N₂ at a pressureof 2.3 Torr. The samples were then unloaded under a flow of 500 sccm N₂,quickly enclosed in a container and then stored under N₂ for shipment tothe vendor for analytical characterization of their properties.

The ‘SC-1 cleaned, HF-etched’ 1,000 Å SiO₂ and Si(100) samples werecharacterized using water contact angle measurements, Atomic ForceMicroscopy (AFM) and Time-of-Flight Secondary Ion Mass Spectrometry(TOF-SIMS). The results of these analyses are presented in the tablebelow.

Contact Angle Measurements and Surface Roughness Measurements WaterThermal Contact Surface Treat- Angle Roughness Sample ment (Degrees)(nm) SC-1 Cleaned, HF-etched No 90.5 0.24 1,000 Å SiO2/Si(100) SC-1Cleaned, HF-etched No 51.8 0.16 Si(100)

The samples were also analyzed by X-Ray Photoelectron Spectroscopy (XPS)and the results are presented in the table below.

Carbon Oxygen Silicon O/Si Sample (atomic %) (atomic %) (atomic %) RatioSC-1 Cleaned, HF-etched 2.4 65.2 32.3 2.02 1,000 Å SiO2/Si(100) SC-1Cleaned, HF-etched 6.2 24.8 68.8 0.36 Si(100)

The TOF-SIMS spectra for the ‘SC-1 cleaned, HF-etched’ 1,000 Å SiO₂ andSi(100) samples are presented in FIG. 24 . Referring to FIG. 24 , thelack of observation of the peaks associated with bis-dimethylsilylethanesurface passivation in the Si(100) TOF-SIMS spectrum is evidence thatthe formation of the passivation layer was limited to the ‘SC-1 cleaned,HF-etched’ 1,000 Å SiO₂/Si(100) substrate. That is, the passivation wasformed selectively on the desired surface and not on the Si(100)surface.

Normalized Ion Intensities for positive ions with mass 45 amu, 29 amu,43 amu, 59 amu and 73 amu for “SC-1 cleaned, HF-etched” 1,000 ÅSiO₂/Si(100) and Si(100) are shown in the table below.

Thermal Sample Treatment mass 45 amu mass 29 amu mass 43 amu mass 59 amumass 73 amu SC-1 Cleaned, HF-etched No 718 333 917 445 127 1,000 ÅSiO2/Si(100) SC-1 Cleaned, HF-etched No 1253 1683 72 1.9 0.4 Si(100)

Example 14 (Comparative): Selective Formation of Bis-DimethylsilylethaneSurface Passivation on ‘as-Received’, 1,000 Å SiO₂/Si(100) and not onSi(100) Using [Cl(CH₃)₂Si]₂(CH₂)₂ (1,2-bis-chlorodimethylsilylethane) at370° C. with Thermal Treatment Processing

Several 1.5″×1.5″ coupons of a 1,000 Å thermal SiO₂/Si(100) [“1,000 ÅSiO₂”) and Si(100) were cleaved from 4″ wafers, blown off with a streamof high purity nitrogen to remove particles.

Several of these ‘as-received’, 1000 Å SiO₂ and “SC-1 cleaned,HF-etched” Si(100) samples were then loaded into the tube of a tubefurnace reactor system under a flow of 250 sccm ultra-high purity N₂ gasat room temperature with as minimum a delay as possible. The tube wasthen sealed and slowly evacuated to a pressure of 80 mTorr. A flow of 20sccm N₂ was then introduced into the reactor tube and a reduced pressureN₂ purge was conducted for 2 minutes (at a pressure of 2.3 Torr). Theflow of N₂ was then stopped and the tube was evacuated to a pressure of≤5 mTorr. The previously described cycle purging steps were repeateduntil the base pressure of the system was achieved.

After base pressure was achieved, a flow of 20 sccm of ultra-high purityN₂ was introduced into the reactor system and a reduced pressure N₂purge (at 2.3 Torr) was conducted for 1 hour to reduce the backgroundmoisture concentration in the system prior to initiating the thermaltreatment. As known to those skilled in the art, use of a load locksystem will enable greatly reduced cycle times while still providing therequired system purity for the processes described herein to beoperative.

The thermal treatment was then performed under a reduced pressure purgeof ultra-high purity N₂ gas (at 2.3 Torr) using the pre-programmedheating process recipe stored on the temperature controller for thefurnace. The heat traces of two independent thermocouples (onerepresenting the external tube temperature—‘wall’ and one representingthe sample temperature) are shown in FIG. 25 .

After the thermal treatment was completed, a flow of 20 sccm ultra-highpurity N₂ was maintained through the tube at a pressure of 2.5 Torrwhile the sample temperature was reduced to 370° C. The samples wereequilibrated at 370° C. for 10 minutes, the N₂ flow was terminated andthe tube was fully evacuated to a pressure of no more than 1 mTorr. Thetube was then charged with a first chemical dose of1,2-bis-chlorodimethylsilylethane [(Cl(CH₃)₂Si]₂(CH₂)₂] to a pressure of0.24 Torr and then isolated at this pressure for 10 minutes. The firstchemical dose was then removed from the chamber using a combination ofreduced pressure N₂ purging and evacuation that encompassed firstintroducing a dynamic flow of 20 sccm N₂ at a pressure of 2.5 Torr forone minute, followed by evacuation of the tube to a pressure not greaterthan 10 mTorr for two minutes. The second chemical dose of(Cl(CH₃)₂Si]₂(CH₂)₂ was then introduced in a manner identical to thefirst dose except that the pressure of the second dose was 0.25 Torr.The second dose was then removed in the same manner as the firstchemical dose prior to the introduction of the third chemical dose. Thethird through twelfth chemical doses of (Cl(CH₃)₂Si]₂(CH₂)₂ were thenintroduced in a manner identical to the first and second doses exceptthat the pressure of these doses varied slightly between 0.24 Torr and0.26 Torr. The third through twelfth doses were then removed in the samemanner as the first and second chemical doses, completing the selectiveformation of the bis-dimethylsilylethane surface passivation on the‘SC-1 cleaned, HF-etched’, 1,000 Å SiO₂ samples, but not on the Si(100)samples.

After the selective passivation formation was completed, the‘as-received’ 1,000 Å SiO₂ and Si(100) samples were cooled to roomtemperature under a flow of 20 sccm ultra-high purity N₂ at a pressureof 2.3 Torr. The samples were then unloaded under a flow of 500 sccm N₂,quickly enclosed in a container and then stored under N₂ for shipment tothe vendor for analytical characterization of their properties.

The ‘as-received’ 1,000 Å SiO₂ and Si(100) samples were characterizedusing water contact angle measurements, Atomic Force Microscopy (AFM)and Time-of-Flight Secondary Ion Mass Spectrometry (TOF-SIMS). Forcomparison, ‘as-received’ 1,000 Å SiO₂ samples that did not receive thethermal treatment processing were also characterized in a similarfashion. The results of these analyses are presented in the tablesbelow:

Contact Angle Measurements and Surface Roughness Measurements WaterThermal Contact Surface Treat- Angle Roughness Sample ment (Degrees)(nm) As-Received 1,000 Å Yes 83.9 0.23 SiO2/Si(100) SC-1 Cleaned,HF-etched Yes 56.4 0.18 Si(100)

The samples were also analyzed by X-Ray Photoelectron Spectroscopy (XPS)and the results are presented in the table below:

Carbon Oxygen Silicon O/ Sample (atomic %) (atomic %) (atomic %) SiRatio As-Received 1,000 Å 2.2 65.7 31.9 2.06 SiO2/Si(100) SC-1 Cleaned,HF-etched 5 28.6 65.7 0.44 Si(100)

The TOF-SIMS spectra for the ‘as-received’ 1,000 Å SiO₂ and Si(100)samples are presented in FIG. 26 . Referring to FIG. 26 , the lack ofobservation of the peaks associated with bis-dimethylsilylethane surfacepassivation in the Si(100) TOF-SIMS spectrum is evidence that theformation of the passivation layer was limited to the ‘as-received’1,000 Å SiO₂/Si(100) substrate. That is, the passivation was formedselectively on the desired surface and not on the Si(100) surface.

Normalized Ion Intensities for positive ions with mass 45 amu, 29 amu,43 amu, 59 amu and 73 amu for “as-received” 1,000 Å SiO₂/Si(100) andSi(100) are shown in the table below.

Thermal Sample Treatment mass 45 amu mass 29 amu mass 43 amu mass 59 amumass 73 amu As-Received 1,000 Å Yes 673 301 630 190 94 SiO2/Si(100) SC-1Cleaned, HF-etched Yes 1200 1527 63 2.2 0.4 Si(100)

Example 15 (Comparative): Selective Formation of Bis-DimethylsilylethaneSurface Passivation on ‘as-Received’, 1,000 Å SiO₂/Si(100) and not onSi(100) Using [Cl(CH₃)₂Si]₂(CH₂)₂ (1,2-bis-chlorodimethylsilylethane) at370° C. without Thermal Treatment Processing

Several 1.5″×1.5″ coupons of a 1,000 Å thermal SiO₂/Si(100) [“1,000 ÅSiO₂”) and Si(100) were cleaved from 4″ wafers, blown off with a streamof high purity nitrogen to remove particles.

Several of these ‘as-received’, 1000 Å SiO₂ and “SC-1 cleaned,HF-etched” Si(100) samples were then loaded into the tube of a tubefurnace reactor system under a flow of 250 sccm ultra-high purity N₂ gasat room temperature with as minimum a delay as possible. The tube wasthen sealed and slowly evacuated to a pressure of 40 mTorr. A flow of 20sccm N₂ was then introduced into the reactor tube and a reduced pressureN₂ purge was conducted for 2 minutes (at a pressure of 2.3 Torr). Theflow of N₂ was then stopped and the tube was evacuated to a pressure of≤5 mTorr. The previously described cycle purging steps were repeateduntil the base pressure of the system was achieved.

After base pressure was achieved, a flow of 20 sccm of ultra-high purityN₂ was introduced into the reactor system and a reduced pressure N₂purge (at 2.3 Torr) was conducted for 1 hour to reduce the backgroundmoisture concentration in the system prior to initiating the thermaltreatment. As known to those skilled in the art, use of a load locksystem will enable greatly reduced cycle times while still providing therequired system purity for the processes described herein to beoperative.

The samples were equilibrated at 370° C. for 10 minutes, the N₂ flow wasterminated and the tube was fully evacuated to a pressure of no morethan 1 mTorr. The tube was then charged with a first chemical dose of1,2-bis-chlorodimethylsilylethane [(Cl(CH₃)₂Si]₂(CH₂)₂] to a pressure of0.23 Torr and then isolated at this pressure for 10 minutes. The firstchemical dose was then removed from the chamber using a combination ofreduced pressure N₂ purging and evacuation that encompassed firstintroducing a dynamic flow of 20 sccm N₂ at a pressure of 2.5 Torr forone minute, followed by evacuation of the tube to a pressure not greaterthan 10 mTorr for two minutes. The second chemical dose of(Cl(CH₃)₂Si]₂(CH₂)₂ was then introduced in a manner identical to thefirst dose except that the pressure of the second dose was 0.23 Torr.The second dose was then removed in the same manner as the firstchemical dose prior to the introduction of the third chemical dose. Thethird through twelfth chemical doses of (Cl(CH₃)₂Si]₂(CH₂)₂ were thenintroduced in a manner identical to the first and second doses exceptthat the pressure of these doses varied slightly between 0.23 Torr and0.25 Torr. The third through twelfth doses were then removed in the samemanner as the first and second chemical doses, completing the selectiveformation of the bis-dimethylsilylethane surface passivation on the‘SC-1 cleaned, HF-etched’, 1,000 Å SiO₂ samples, but not on the Si(100)samples.

After the selective passivation formation was completed, the‘as-received’ 1,000 Å SiO₂ and Si(100) samples were cooled to roomtemperature under a flow of 20 sccm ultra-high purity N₂ at a pressureof 2.3 Torr. The samples were then unloaded under a flow of 500 sccm N₂,quickly enclosed in a container and then stored under N₂ for shipment tothe vendor for analytical characterization of their properties.

The ‘as-received’ 1,000 Å SiO₂ and Si(100) samples were characterizedusing water contact angle measurements, Atomic Force Microscopy (AFM)and Time-of-Flight Secondary Ion Mass Spectrometry (TOF-SIMS). Forcomparison, ‘as-received’ 1,000 Å SiO₂ samples that did not receive thethermal treatment processing were also characterized in a similarfashion. The results of these analyses are presented in the table below.

Contact Angle Measurements and Surface Roughness Measurements WaterThermal Contact Surface Treat- Angle Roughness Sample ment (Degrees)(nm) As-Received 1,000 Å No 83.7 0.21 1,000 Å SiO2/Si(100) SC-1 Cleaned,HF-etched No 51.8 0.16 Si(100)

The samples were also analyzed by X-Ray Photoelectron Spectroscopy (XPS)and the results are presented in the table below.

Carbon Oxygen Silicon O/Si Sample (atomic %) (atomic %) (atomic %) RatioAs-Received 1,000 Å 2.3 65.6 32.3 2.04 SiO2/Si(100) SC-1 Cleaned,HF-etched 6.2 24.8 68.8 0.36 Si(100)

The TOF-SIMS spectra for the ‘as-received’ 1,000 Å SiO₂ and Si(100)samples are presented in FIG. 27 . Referring to FIG. 27 , the lack ofobservation of the peaks associated with bis-dimethylsilylethane surfacepassivation in the Si(100) TOF-SIMS spectrum is evidence that theformation of the passivation layer was limited to the ‘as-received’1,000 Å SiO₂/Si(100) substrate. That is, the passivation was formedselectively on the desired surface and not on the Si(100) surface.

Normalized Ion Intensities for positive ions with mass 45 amu, 29 amu,43 amu, 59 amu and 73 amu or “as-received” 1,000 Å SiO₂/Si(100) andSi(100) are shown in the table below.

Thermal Sample Treatment mass 45 amu mass 29 amu mass 43 amu mass 59 amumass 73 amu As-Received 1,000 Å No 710 351 810 253 115 SiO2/Si(100) SC-1Cleaned, HF-etched No 1253 1683 72 1.9 0.4 Si(100)

Example 16 (Comparative): Selective Formation of Trimethylsilyl SurfacePassivation on ‘SC-1 Cleaned, HF-Etched’, 1,000 Å SiO₂/Si(100) and noton Si(100) Using (CH₃)₂NSi(CH₃)₃ (Dimethylaminotrimethylsilane) at 270°C. with 515° C. Thermal Treatment

Several 1.5″×1.5″ coupons of a 1,000 Å thermal SiO₂/Si(100) [“1,000 ÅSiO₂”) and Si(100) were cleaved from 4″ wafers, blown off with a streamof high purity nitrogen to remove particles and then loaded into aTeflon boat suitable for immersion in an SC-1 cleaning bath. The boatand samples were then immersed in an SC-1 cleaning solution (100 mlultra-high purity NH₄OH (28%-30%); 200 ml ultra-high purity H₂O₂(28-30%); 1000 ml distilled, deionized H₂O) that was pre-heated to atemperature of 70+/−5° C. where they were cleaned for 10 minutes. TheSC-1 cleaned, 1,000 Å SiO₂/Si(100) and Si(100) samples were then removedfrom the cleaning bath and rinsed of chemicals using three dump rinsecycles of distilled, deionized water. The samples were then driedthoroughly using a source of ultra-high purity N₂ gas that was filteredfor particles.

The dried SC-1 cleaned samples were then placed into a Teflon boatsuitable for immersion in an HF-etch batch. The boat and samples werethen immersed in an HF-etch bath (51 ml ultra-high purity HF (48-49%);1000 ml distilled, deionized H₂O) that was at 21+/−2° C. where they wereetched for 90 seconds. The ‘SC-1 cleaned, HF-etched’, 1,000 ÅSiO₂/Si(100) and Si(100) samples were then removed from the HF solutionand quickly immersed in distilled, de-ionized water and then driedthoroughly using a source of ultra-high purity N₂ gas that was filteredfor particles.

Several of the ‘SC-1 cleaned, HF-etched’, 1000 Å SiO₂ and Si(100)samples were then loaded into the tube of a tube furnace reactor systemunder a flow of 250 sccm ultra-high purity N₂ gas at room temperaturewith as minimum a delay as possible. The tube was then sealed and slowlyevacuated to a pressure of 80 mTorr. A flow of 20 sccm N₂ was thenintroduced into the reactor tube and a reduced pressure N₂ purge wasconducted for 2 minutes (at a pressure of 2.3 Torr). The flow of N₂ wasthen stopped and the tube was evacuated to a pressure of ≤5 mTorr. Thepreviously described cycle purging steps were repeated until the basepressure of the system was achieved.

After base pressure was achieved, a flow of 20 sccm of ultra-high purityN₂ was introduced into the reactor system and a reduced pressure N₂purge (at 2.3 Torr) was conducted for 1 hour to reduce the backgroundmoisture concentration in the system prior to initiating the thermaltreatment. As known to those skilled in the art, use of a load locksystem will enable greatly reduced cycle times while still providing therequired system purity for the processes described herein to beoperative.

A 515° C. thermal treatment was then performed under a reduced pressurepurge of ultra-high purity N₂ gas (at 2.3 Torr) by ramping the samplesto 515° C. at the maximum ramping rate of the furnace (ca. 20°C./minute).

After the thermal treatment was completed, a flow of 20 sccm ultra-highpurity N₂ was maintained through the tube at a pressure of 2.5 Torrwhile the sample temperature was reduced to 270° C. The samples wereequilibrated at 270° C. for 10 minutes, the N₂ flow was terminated andthe tube was fully evacuated to a pressure of no more than 1 mTorr. Thetube was then charged with a first chemical dose ofdimethylaminotrimethylsilane [(CH₃)₂NSi(CH₃)₃] to a pressure of 20.0Torr and then isolated at this pressure for 20 minutes. The firstchemical dose was then removed from the chamber using a combination ofreduced pressure N₂ purging and evacuation that encompassed firstintroducing a dynamic flow of 20 sccm N₂ at a pressure of 2.5 Torr forone minute, followed by evacuation of the tube to a pressure not greaterthan 10 mTorr for two minutes. The second chemical dose of(CH₃)₂NSi(CH₃)₃ was then introduced in a manner identical to the firstdose except that the pressure of the second dose was 20.8 Torr. Thesecond dose was then removed in the same manner as the first chemicaldose prior to the introduction of the third chemical dose. The thirdchemical dose of (CH₃)₂NSi(CH₃)₃ was then introduced in a manneridentical to the first and second doses except that the pressure of thethird dose was 20.0 Torr. The third chemical dose was then removed inthe same manner as the first and second chemical doses, completing theselective formation of the trimethylsilyl surface passivation on the‘SC-1 cleaned, HF-etched’, 1,000 Å SiO₂ samples, but not on the Si(100)samples.

After the selective passivation formation was completed, the ‘SC-1cleaned, HF-etched’ 1,000 Å SiO₂ and Si(100) samples were cooled to roomtemperature under a flow of 20 sccm ultra-high purity N₂ at a pressureof 2.3 Torr. The samples were then unloaded under a flow of 500 sccm N₂,quickly enclosed in a container and then stored under N₂ for shipment tothe vendor for analytical characterization of their properties.

The ‘SC-1 cleaned, HF-etched’ 1,000 Å SiO₂ and Si(100) samples werecharacterized using water contact angle measurements, Atomic ForceMicroscopy (AFM) and Time-of-Flight Secondary Ion Mass Spectrometry(TOF-SIMS). For comparison, ‘As-received’ 1,000 Å SiO₂ samples were alsocharacterized in a similar fashion. The results of these analyses arepresented in the tables below:

Contact Angle Measurements and Surface Roughness Measurements ThermalWater Treat- Contact Surface ment Angle Roughness Sample (515° C.)(Degrees) (nm) As-Received 1,000 Å Yes 76.1 0.32 SiO2/Si(100) SC-1Cleaned, HF-etched Yes 51.8 0.34 1,000 Å SiO2/Si(100) SC-1 Cleaned,HF-etched Yes 28.2 0.18 Si(100)

The samples were also analyzed by X-Ray Photoelectron Spectroscopy (XPS)and the results are presented in the table below:

Carbon Oxygen Silicon O/ Sample (atomic %) (atomic %) (atomic %) SiRatio As-Received 1,000 Å 3.4 65.4 31 2.11 SiO2/Si(100) SC-1 Cleaned,HF-etched 2 66.5 31.2 2.12 1,000 Å SiO2/Si(100) SC-1 Cleaned, HF-etched4.4 34.9 60.3 0.58 Si(100)

The TOF-SIMS spectra for the ‘SC-1 cleaned, HF-etched’ 1,000 Å SiO₂, the‘as-received’ 1,000 Å SiO₂ and Si(100) samples are presented in FIGS. 28to 30 . Referring to FIGS. 28 to 30 , the lack of observation of thepeaks associated with trimethylsilyl surface passivation in the Si(100)TOF-SIMS spectrum is evidence that the formation of the passivationlayer was limited to the ‘SC-1 cleaned, HF-etched’ 1,000 Å SiO₂/(100)substrate. That is, the passivation was formed selectively on thedesired surface and not on the Si(100) surface.

Normalized Ion Intensities for positive ions with mass 45 amu, 29 amu,43 amu, 59 amu and 73 amu for “SC-1 cleaned, HF-etched” 1,000 ÅSiO₂/Si(100) and Si(100) are shown in the table below.

Thermal Treatment Sample (515° C.) mass 45 amu mass 29 amu mass 43 amumass 59 amu mass 73 amu As-Received 1,000 Å Yes 490 284 627 636 357SiO2/Si(100) SC-1 Cleaned, HF-etched Yes 630 348 757 87 262 1000 ÅSiO2/Si(100) SC-1 Cleaned, HF-etched Yes 1650 1380 54 15 3 Si(100)

Example 17: Selective Formation ofbis-dimethylsilylethane/trimethylsilyl Surface Passivation on ‘SC-1Cleaned, HF-Etched’, 1,000 Å SiO₂/Si(100) and on ‘as-Received’, 1,000 ÅSiO₂/Si(100) Using[Cl(CH₃)₂Si]₂(CH₂)₂(1,2-bis-chlorodimethylsilylethane) and(CH₃)₂NSi(CH₃)₃ (Dimethylaminotrimethylsilane) at 370° C. with ThermalTreatment Processing

Several 1.5″×1.5″ coupons of a 1,000 Å thermal SiO₂/Si(100) [“1,000 ÅSiO₂”) and Si(100) were cleaved from 4″ wafers, blown off with a streamof high purity nitrogen to remove particles and then some of them werethen loaded into a Teflon boat suitable for immersion in an SC-1cleaning bath. The boat and samples were then immersed in an SC-1cleaning solution (100 ml ultra-high purity NH₄OH (28%-30%); 200 mlultra-high purity H₂O₂ (28-30%); 1000 ml distilled, deionized H₂O) thatwas pre-heated to a temperature of 70+/−5° C. where they were cleanedfor 10 minutes. The SC-1 cleaned, 1,000 Å SiO₂/Si(100) and Si(100)samples were then removed from the cleaning bath and rinsed of chemicalsusing three dump rinse cycles of distilled, deionized water. The sampleswere then dried thoroughly using a source of ultra-high purity N₂ gasthat was filtered for particles.

The dried SC-1 cleaned samples were then placed into a Teflon boatsuitable for immersion in an HF-etch batch. The boat and samples werethen immersed in an HF-etch bath (51 ml ultra-high purity HF (48-49%);1000 ml distilled, deionized H₂O) that was at 21+/−2° C. where they wereetched for 90 seconds. The ‘SC-1 cleaned, HF-etched’, 1,000 ÅSiO₂/Si(100) and Si(100) samples were then removed from the HF solutionand quickly immersed in distilled, de-ionized water and then driedthoroughly using a source of ultra-high purity N₂ gas that was filteredfor particles.

Several of the ‘SC-1 cleaned, HF-etched’, 1000 Å SiO₂ and ‘as-received’,1,000 Å SiO₂/Si(100) samples were then loaded into the tube of a tubefurnace reactor system under a flow of 250 sccm ultra-high purity N₂ gasat room temperature with as minimum a delay as possible. The tube wasthen sealed and slowly evacuated to a pressure of 8060 mTorr. A flow of20 sccm N₂ was then introduced into the reactor tube and a reducedpressure N₂ purge was conducted for 2 minutes (at a pressure of 2.3Torr). The flow of N₂ was then stopped and the tube was evacuated to apressure of ≤5 mTorr. The previously described cycle purging steps wererepeated until the base pressure of the system was achieved.

After base pressure was achieved, a flow of 20 sccm of ultra-high purityN₂ was introduced into the reactor system and a reduced pressure N₂purge (at 2.3 Torr) was conducted for 1 hour to reduce the backgroundmoisture concentration in the system prior to initiating the thermaltreatment. As known to those skilled in the art, use of a load locksystem will enable greatly reduced cycle times while still providing therequired system purity for the processes described herein to beoperative.

The thermal treatment was then performed under a reduced pressure purgeof ultra-high purity N₂ gas (at 2.3 Torr) using the pre-programmedheating process recipe stored on the temperature controller for thefurnace. The heat traces of two independent thermocouples (onerepresenting the external tube temperature—‘wall’ and one representingthe sample temperature) are shown in FIG. 31 .

After the thermal treatment was completed, a flow of 20 sccm ultra-highpurity N₂ was maintained through the tube at a pressure of 2.5 Torrwhile the sample temperature was reduced to 370° C. The samples wereequilibrated at 370° C. for 10 minutes, the N₂ flow was terminated andthe tube was fully evacuated to a pressure of no more than 1 mTorr. Thetube was then charged with a first chemical dose of1,2-bis-chlorodimethylsilylethane [(Cl(CH₃)₂Si]₂(CH₂)₂] to a pressure of0.25 Torr and then isolated at this pressure for 10 minutes. The firstchemical dose was then removed from the chamber using a combination ofreduced pressure N₂ purging and evacuation that encompassed firstintroducing a dynamic flow of 20 sccm N₂ at a pressure of 2.5 Torr forone minute, followed by evacuation of the tube to a pressure not greaterthan 10 mTorr for two minutes. The second chemical dose of(Cl(CH₃)₂Si]₂(CH₂)₂ was then introduced in a manner identical to thefirst dose except that the pressure of the second dose was 0.25 Torr.The second dose was then removed in the same manner as the firstchemical dose prior to the introduction of the third chemical dose. Thethird through twelfth chemical doses of (Cl(CH₃)₂Si]₂(CH₂)₂ were thenintroduced in a manner identical to the first and second doses exceptthat the pressure of these doses varied slightly between 0.25 Torr and0.26 Torr. The third through twelfth doses were then removed in the samemanner as the first and second chemical doses. The reactor tube was thenevacuated to base pressure over a period of 15 minutes prior to thestart of chemical dosing with dimethylaminotrimethylsilane. The tube wasthen charged with a first chemical dose of dimethylaminotrimethylsilane[(CH₃)₂NSi(CH₃)₃] to a pressure of 20.4 Torr and then isolated at thispressure for 10 minutes. The first chemical dose was then removed fromthe chamber using a combination of reduced pressure N₂ purging andevacuation that encompassed first introducing a dynamic flow of 20 sccmN₂ at a pressure of 2.5 Torr for one minute, followed by evacuation ofthe tube to a pressure not greater than 10 mTorr for two minutes. Thesecond chemical dose of (CH₃)₂NSi(CH₃)₃ was then introduced in a manneridentical to the first dose except that the pressure of the second dosewas 20.3 Torr. The second dose was then removed in the same manner asthe first chemical dose prior to the introduction of the third chemicaldose. The third chemical dose of (CH₃)₂NSi(CH₃)₃ was then introduced ina manner identical to the first and second doses except that thepressure of the third dose was 19.8 Torr. The third chemical dose wasthen removed in the same manner as the first and second chemical doses,completing the selective formation of the trimethylsilyl surfacepassivation on the ‘SC-1 cleaned, HF-etched’, 1,000 Å SiO₂ samples and‘as-received’ 1,000 Å SiO₂ samples.

After the selective passivation formation was completed, the ‘SC-1cleaned, HF-etched’ 1,000 Å SiO₂ and ‘as-received’ 1,000 Å SiO₂ sampleswere cooled to room temperature under a flow of 20 sccm ultra-highpurity N₂ at a pressure of 2.3 Torr. The samples were then unloadedunder a flow of 500 sccm N₂, quickly enclosed in a container and thenstored under N₂ for shipment to the vendor for analyticalcharacterization of their properties.

The ‘SC-1 cleaned, HF-etched’ 1,000 Å SiO₂ and ‘as-received’ 1,000 ÅSiO₂ samples were characterized using water contact angle measurements,Atomic Force Microscopy (AFM) and Time-of-Flight Secondary Ion MassSpectrometry (TOF-SIMS). The results of these analyses are presented inthe table below and in FIG. 32 .

Contact Angle Measurements and Surface Roughness Measurements WaterSurface Thermal Contact Angle Roughness Sample Treatment (Degrees) (nm)As-Received 1,000 Å No 94 0.24 SiO2/Si(100) SC-1 Cleaned, HF-etched No98.8 0.3 1,000 Å SiO2/Si(100)

The samples were also analyzed by X-Ray Photoelectron Spectroscopy (XPS)and the results are presented in the table below:

Carbon Oxygen Silicon Sample (atomic %) (atomic %) (atomic %) O/Si RatioAs-Received 1,000 Å 5 64.6 30.4 2.125 SiO2/Si(100) SC-1 Cleaned,HF-etched 4.4 65 30.7 2.117263844 1,000 Å SiO2/Si(100)

Referring to FIG. 32 , it is clear from the spectra that there is a muchhigher surface coverage of passivating species on the “SC-1 cleaned,HF-etched” 1,000 Å SiO₂/Si(100) sample relative to the ‘as-received’1,000 Å SiO₂ sample. The distributions of positive ions from each sampleare consistent with the presence of both bis-dimethylsilylethane andtrimethylsilyl passivating species as can be inferred from comparisonwith the TOF-SIMS spectra for samples that were treated withbis-dimethylsilylethane and trimethylsilyl precursor compounds (Examples10 and 15).

Normalized ion intensities for positive ions with mass 45 amu, 29 amu,43 amu, 59 amu and 73 amu for “SC-1 cleaned, HF-etched” 1,000 ÅSiO₂/Si(100) and ‘as-received’ 1,000 Å SiO₂ samples are presented in thetable below.

Thermal Sample Treatment mass 45 amu mass 29 amu mass 43 amu mass 59 amumass 73 amu As-Received 1000 Å Yes 533 389 895 226 318 SiO2/Si(100) SC-1Cleaned, HF-etched Yes 733 405.3 1000 315 218 1,000 Å SiO2/Si(100)

Example 18: Selective Formation ofbis-dimethylsilylethane/trimethylsilyl Surface Passivation on ‘SC-1Cleaned, HF-Etched’, 1,000 Å SiO₂/Si(100) and not on Si(100) Using[Cl(CH₃)₂Si]₂(CH₂)₂ (1,2-bis-chlorodimethylsilylethane) and(CH₃)₂NSi(CH₃)₃ (Dimethylaminotrimethylsilane) at 370° C. withoutThermal Treatment Processing

Several 1.5″×1.5″ coupons of a 1,000 Å thermal SiO₂/Si(100) [“1,000 ÅSiO₂”) and Si(100) were cleaved from 4″ wafers, blown off with a streamof high purity nitrogen to remove particles and then some of them werethen loaded into a Teflon boat suitable for immersion in an SC-1cleaning bath. The boat and samples were then immersed in an SC-1cleaning solution (100 ml ultra-high purity NH₄OH (28%-30%); 200 mlultra-high purity H₂O₂ (28-30%); 1000 ml distilled, deionized H₂O) thatwas pre-heated to a temperature of 70+/−5° C. where they were cleanedfor 10 minutes. The SC-1 cleaned, 1,000 Å SiO₂/Si(100) and Si(100)samples were then removed from the cleaning bath and rinsed of chemicalsusing three dump rinse cycles of distilled, deionized water. The sampleswere then dried thoroughly using a source of ultra-high purity N₂ gasthat was filtered for particles.

The dried SC-1 cleaned samples were then placed into a Teflon boatsuitable for immersion in an HF-etch batch. The boat and samples werethen immersed in an HF-etch bath (51 ml ultra-high purity HF (48-49%);1000 ml distilled, deionized H₂O) that was at 21+/−2° C. where they wereetched for 90 seconds. The ‘SC-1 cleaned, HF-etched’, 1,000 ÅSiO₂/Si(100) and Si(100) samples were then removed from the HF solutionand quickly immersed in distilled, de-ionized water and then driedthoroughly using a source of ultra-high purity N₂ gas that was filteredfor particles.

Several of the ‘SC-1 cleaned, HF-etched’, 1000 Å SiO₂ and ‘as-received’,1,000 Å SiO₂/Si(100) samples were then loaded into the tube of a tubefurnace reactor system under a flow of 250 sccm ultra-high purity N₂ gasat room temperature with as minimum a delay as possible. The tube wasthen sealed and slowly evacuated to a pressure of 8060 mTorr. A flow of20 sccm N₂ was then introduced into the reactor tube and a reducedpressure N₂ purge was conducted for 2 minutes (at a pressure of 2.3Torr). The flow of N₂ was then stopped and the tube was evacuated to apressure of ≤5 mTorr. The previously described cycle purging steps wererepeated until the base pressure of the system was achieved.

After base pressure was achieved, a flow of 20 sccm of ultra-high purityN₂ was introduced into the reactor system and a reduced pressure N₂purge (at 2.3 Torr) was conducted for 1 hour to reduce the backgroundmoisture concentration in the system prior to initiating the thermaltreatment. As known to those skilled in the art, use of a load locksystem will enable greatly reduced cycle times while still providing therequired system purity for the processes described herein to beoperative.

Under a flow of 20 sccm ultra-high purity N₂ through the tube at apressure of 2.5 Torr while the sample temperature was raised to 370° C.The samples were equilibrated at 370° C. for 10 minutes, the N₂ flow wasterminated and the tube was fully evacuated to a pressure of no morethan 1 mTorr. The tube was then charged with a first chemical dose of1,2-bis-chlorodimethylsilylethane [(Cl(CH₃)₂Si]₂(CH₂)₂] to a pressure of0.25 Torr and then isolated at this pressure for 10 minutes. The firstchemical dose was then removed from the chamber using a combination ofreduced pressure N₂ purging and evacuation that encompassed firstintroducing a dynamic flow of 20 sccm N₂ at a pressure of 2.5 Torr forone minute, followed by evacuation of the tube to a pressure not greaterthan 10 mTorr for two minutes. The second chemical dose of(Cl(CH₃)₂Si]₂(CH₂)₂ was then introduced in a manner identical to thefirst dose except that the pressure of the second dose was 0.26 Torr.The second dose was then removed in the same manner as the firstchemical dose prior to the introduction of the third chemical dose. Thethird through twelfth chemical doses of (Cl(CH₃)₂Si]₂(CH₂)₂ were thenintroduced in a manner identical to the first and second doses exceptthat the pressure of these doses varied slightly between 0.25 Torr and0.26 Torr. The third through twelfth doses were then removed in the samemanner as the first and second chemical doses. The reactor tube was thenevacuated to base pressure over a period of 15 minutes prior to thestart of chemical dosing with dimethylaminotrimethylsilane. The tube wasthen charged with a first chemical dose of dimethylaminotrimethylsilane[(CH₃)₂NSi(CH₃)₃] to a pressure of 20.4 Torr and then isolated at thispressure for 10 minutes. The first chemical dose was then removed fromthe chamber using a combination of reduced pressure N₂ purging andevacuation that encompassed first introducing a dynamic flow of 20 sccmN₂ at a pressure of 2.5 Torr for one minute, followed by evacuation ofthe tube to a pressure not greater than 10 mTorr for two minutes. Thesecond chemical dose of (CH₃)₂NSi(CH₃)₃ was then introduced in a manneridentical to the first dose except that the pressure of the second dosewas 20.3 Torr. The second dose was then removed in the same manner asthe first chemical dose prior to the introduction of the third chemicaldose. The third chemical dose of (CH₃)₂NSi(CH₃)₃ was then introduced ina manner identical to the first and second doses except that thepressure of the third dose was 19.8 Torr. The third chemical dose wasthen removed in the same manner as the first and second chemical doses,completing the selective formation of the trimethylsilyl surfacepassivation on the ‘SC-1 cleaned, HF-etched’, 1,000 Å SiO₂ samples and‘as-received’ 1,000 Å SiO₂ samples.

After the selective passivation formation was completed, the ‘SC-1cleaned, HF-etched’ 1,000 Å SiO₂ and ‘as-received’ 1,000 Å SiO₂ sampleswere cooled to room temperature under a flow of 20 sccm ultra-highpurity N₂ at a pressure of 2.3 Torr. The samples were then unloadedunder a flow of 500 sccm N₂, quickly enclosed in a container and thenstored under N₂ for shipment to the vendor for analyticalcharacterization of their properties.

The ‘SC-1 cleaned, HF-etched’ 1,000 Å SiO₂ and ‘as-received’ 1,000 ÅSiO₂ samples were characterized using water contact angle measurements,Atomic Force Microscopy (AFM) and Time-of-Flight Secondary Ion MassSpectrometry (TOF-SIMS). The results of these analyses are presented inthe table below and FIG. 33 .

Contact Angle Measurements and Surface Roughness Measurements WaterSurface Thermal Contact Angle Roughness Sample Treatment (Degrees) (nm)As-Received 1,000 Å Yes 95 0.23 SiO2/Si(100) SC-1 Cleaned, HF-etched Yes99.6 0.32 1,000 Å SiO2/Si(100)

The samples were also analyzed by X-Ray Photoelectron Spectroscopy (XPS)and the results are presented in the table below.

Carbon Oxygen Silicon Sample (atomic %) (atomic %) (atomic %) O/Si RatioAs-Received 1,000 Å 4.8 64.9 30.4 2.134868421 SiO2/Si(100) SC-1 Cleaned,HF-etched 4.5 65 30.5 2.131147541 1,000 Å SiO2/Si(100)

Referring to FIG. 33 , it is clear from the spectra that there is a muchhigher surface coverage of passivating species on the “SC-1 cleaned,HF-etched” 1,000 Å SiO₂/(100) sample relative to the ‘as-received’ 1,000Å SiO₂ sample. The distributions of positive ions from each sample areconsistent with the presence of both bis-dimethylsilylethane andtrimethylsilyl passivating species as can be inferred from comparisonwith the TOF-SIMS spectra for samples that were treated withbis-dimethylsilylethane and trimethylsilyl precursor compounds (Examples10-15).

Normalized ion intensities for positive ions with mass 45 amu, 29 amu,43 amu, 59 amu and 73 amu or “SC-1 cleaned, HF-etched” 1,000 ÅSiO₂/Si(100) and ‘as-received’ 1,000 Å SiO₂ samples are presented in thetable below.

Thermal Sample Treatment mass 45 amu mass 29 amu mass 43 amu mass 59 amumass 73 amu As-Received 1,000 Å No 554 379 961 262 371 SiO2/Si(100) SC-1Cleaned, HF-etched No 615 412 1233 467 697 1,000 Å SiO2/Si(100)

Example 19: Selective Formation of tri-n-propylsilyl Surface Passivationon ‘SC-1 Cleaned, HF-Etched’, 1,000 Å SiO₂/Si(100), “as-Received” 1,000Å SiO₂/Si(100) and not on Si(100) Using (CH₃)₂NSi(CH₂CH₂CH₃)₃(dimethylaminotri-n-propylsilane) at 270° C. with Thermal TreatmentProcessing

The “SC-1 cleaned, HF-etched” 1,000 Å SiO₂ samples were subjected to thesame processes as described for the samples in Example 12 prior to theformation of the passivation layer. A tri-n-propylsilyl passivationlayer was then selectively formed on the “SC-1 cleaned, HF-etched” 1,000Å SiO₂ samples, but not on the “SC-1 cleaned, HF-etched” Si(100) samplesusing the following process.

After the thermal treatment was completed, a flow of 20 sccm ultra-highpurity N₂ was maintained through the tube at a pressure of 2.5 Torrwhile the sample temperature was reduced to 270° C. The samples wereequilibrated at 270° C. for 10 minutes, the N₂ flow was terminated andthe tube was fully evacuated to a pressure of no more than 1 mTorr. Thetube was then charged with a first chemical dose ofdimethylamino(tri-n-propyl) silane (CH₃CH₂CH₂)₃SiN(CH₃)₂ to a pressureof 0.089 Torr and then isolated at this pressure for 10 minutes. Thefirst chemical dose was then removed from the chamber using acombination of reduced pressure N₂ purging and evacuation thatencompassed first introducing a dynamic flow of 20 sccm N₂ at a pressureof 2.5 Torr for one minute, followed by evacuation of the tube to apressure not greater than 10 mTorr for two minutes. The second chemicaldose of (CH₃CH₂CH₂)₃SiN(CH₃)₂ was then introduced in a manner identicalto the first dose except that the pressure of the second dose was 0.073Torr. The second dose was then removed in the same manner as the firstchemical dose prior to the introduction of the third chemical dose. Thethird through eleventh chemical doses of (CH₃CH₂CH₂)₃SiN(CH₃)₂ were thenintroduced in a manner identical to the first and second doses exceptthat the pressure of these doses varied slightly between 0.070 Torr and0.090 Torr. The third through eleventh doses were then removed in thesame manner as the first and second chemical doses, completing theselective formation of the tri-n-propylsilyl surface passivation on the‘SC-1 cleaned, HF-etched’, 1,000 Å SiO₂ samples and ‘as-received’ 1,000Å SiO₂ samples.

After the selective passivation formation was completed, the ‘SC-1cleaned, HF-etched’ 1,000 Å SiO₂ and ‘as-received’ 1,000 Å SiO₂ sampleswere cooled to room temperature under a flow of 20 sccm ultra-highpurity N₂ at a pressure of 2.3 Torr. The samples were then unloadedunder a flow of 500 sccm N₂, quickly enclosed in a container and thenstored under N₂ for shipment to the vendor for analyticalcharacterization of their properties.

The ‘SC-1 cleaned, HF-etched’ 1,000 Å SiO₂ and ‘as-received’ 1,000 ÅSiO₂ samples were characterized using water contact angle measurements,Atomic Force Microscopy (AFM) and Time-of-Flight Secondary Ion MassSpectrometry (TOF-SIMS). The results of these analyses are presented inthe table below and FIG. 34 :

Contact Angle Measurements and Surface Roughness Measurements WaterSurface Thermal Contact Angle Roughness Sample Treatment (Degrees) (nm)As-Received 1,000 Å Yes 98.9 0.22 SiO2/Si(100) SC-1 Cleaned, HF-etchedYes 95.4 0.29 1,000 Å SiO2/Si(100)

The samples were also analyzed by X-Ray Photoelectron Spectroscopy (XPS)and the results are presented in the table below:

Carbon Oxygen Silicon Sample (atomic %) (atomic %) (atomic %) O/Si RatioAs-Received 1,000 Å 4.8 65.3 30.5 2.140983607 SiO2/Si(100) SC-1 Cleaned,HF-etched 4.2 65.1 30.5 2.13442623 1,000 Å SiO2/Si(100)

The TOF-SIMS spectra for the ‘SC-1 cleaned, HF-etched’ 1,000 Å SiO₂ andthe ‘as-received’ 1,000 Å SiO₂ samples are shown in FIG. 34 . It isclear from the spectra that there is a much higher surface coverage ofpassivating species on the “SC-1 cleaned, HF-etched” 1,000 ÅSiO₂/Si(100) sample relative to the ‘as-received’ 1,000 Å SiO₂ sample.

Normalized ion intensities for positive ions with mass 45 amu, 29 amu,43 amu, 59 amu and 73 amu for “SC-1 cleaned, HF-etched” 1,000 ÅSiO₂/Si(100) and ‘as-received’ 1,000 Å SiO₂ samples are presented in thetable below.

Thermal Sample Treatment mass 45 amu mass 29 amu mass 43 amu mass 59 amumass 73 amu As-Received 1,000 Å Yes 489 325 502 115 202.3 SiO2/Si(100)SC-1 Cleaned, HF-etched Yes 489 243 482 155 254 1,000 Å SiO2/Si(100)

Example 20: Selective Formation of tri-n-propylsilyl Surface Passivationon ‘SC-1 Cleaned, HF-Etched’, 1,000 Å SiO₂/Si(100), “as-Received” 1,000Å SiO₂/Si(100) and not on Si(100) Using (CH₃)₂NSi(CH₂CH₂CH₃)₃(dimethylaminotri-n-propylsilane) at 270° C. without Thermal TreatmentProcessing

The “SC-1 cleaned, HF-etched” 1,000 Å SiO₂ samples were subjected to thesame processes as described for the samples in Example 13 prior to theformation of the passivation layer. A tri-n-propylsilyl passivationlayer was then selectively formed on the “SC-1 cleaned, HF-etched” 1,000Å SiO₂ samples, but not on the “SC-1 cleaned, HF-etched” Si(100) samplesusing the following process.

Several of the ‘SC-1 cleaned, HF-etched’, 1000 Å SiO₂ and ‘as-received’,1,000 Å SiO₂/Si(100) samples were then loaded into the tube of a tubefurnace reactor system under a flow of 250 sccm ultra-high purity N₂ gasat room temperature with as minimum a delay as possible. The tube wasthen sealed and slowly evacuated to a pressure of 60 mTorr. A flow of 20sccm N₂ was then introduced into the reactor tube and a reduced pressureN₂ purge was conducted for 2 minutes (at a pressure of 2.3 Torr). Theflow of N₂ was then stopped and the tube was evacuated to a pressure of≤5 mTorr. The previously described cycle purging steps were repeateduntil the base pressure of the system was achieved.

After base pressure was achieved, a flow of 20 sccm of ultra-high purityN₂ was introduced into the reactor system and a reduced pressure N₂purge (at 2.3 Torr) was conducted for 1 hour to reduce the backgroundmoisture concentration in the system prior to initiating the thermaltreatment. As known to those skilled in the art, use of a load locksystem will enable greatly reduced cycle times while still providing therequired system purity for the processes described herein to beoperative.

Under a flow of 20 sccm ultra-high purity N₂ through the tube at apressure of 2.5 Torr while the sample temperature was raised to 270° C.The samples were equilibrated at 270° C. for 10 minutes, the N₂ flow wasterminated and the tube was fully evacuated to a pressure of no morethan 1 mTorr. The tube was then charged with a first chemical dose ofdimethylamino(tri-n-propyl) silane (CH₃CH₂CH₂)₃SiN(CH₃)₂ to a pressureof 0.085 Torr and then isolated at this pressure for 10 minutes. Thefirst chemical dose was then removed from the chamber using acombination of reduced pressure N₂ purging and evacuation thatencompassed first introducing a dynamic flow of 20 sccm N₂ at a pressureof 2.5 Torr for one minute, followed by evacuation of the tube to apressure not greater than 10 mTorr for two minutes. The second chemicaldose of (CH₃CH₂CH₂)₃SiN(CH₃)₂ was then introduced in a manner identicalto the first dose except that the pressure of the second dose was 0.079Torr. The second dose was then removed in the same manner as the firstchemical dose prior to the introduction of the third chemical dose. Thethird through eleventh chemical doses of (CH₃CH₂CH₂)₃SiN(CH₃)₂ were thenintroduced in a manner identical to the first and second doses exceptthat the pressure of these doses varied slightly between 0.081 Torr and0.084 Torr. The third through eleventh doses were then removed in thesame manner as the first and second chemical doses, completing theselective formation of the tri-n-propylsilyl surface passivation on the‘SC-1 cleaned, HF-etched’, 1,000 Å SiO₂ samples and ‘as-received’ 1,000Å SiO₂ samples.

After the selective passivation formation was completed, the ‘SC-1cleaned, HF-etched’ 1,000 Å SiO₂ and ‘as-received’ 1,000 Å SiO₂ sampleswere cooled to room temperature under a flow of 20 sccm ultra-highpurity N₂ at a pressure of 2.3 Torr. The samples were then unloadedunder a flow of 500 sccm N₂, quickly enclosed in a container and thenstored under N₂ for shipment to the vendor for analyticalcharacterization of their properties.

The ‘SC-1 cleaned, HF-etched’ 1,000 Å SiO₂ and ‘as-received’ 1,000 ÅSiO₂ samples were characterized using water contact angle measurements,Atomic Force Microscopy (AFM) and Time-of-Flight Secondary Ion MassSpectrometry (TOF-SIMS). The results of these analyses are presented inthe tables below:

Contact Angle Measurements and Surface Roughness Measurements WaterSurface Thermal Contact Angle Roughness Sample Treatment (Degrees) (nm)As-Received 1,000 Å No 101.5 0.18 SiO2/Si(100) SC-1 Cleaned, HF-etchedNo 94.5 0.29 1,000 Å SiO2/Si(100)

The samples were also analyzed by X-Ray Photoelectron Spectroscopy (XPS)and the results are presented in the table below.

Carbon Oxygen Silicon Sample (atomic %) (atomic %) (atomic %) O/Si RatioAs-Received 1,000 Å 4.1 65.5 30.4 2.154605263 SiO2/Si(100) SC-1 Cleaned,HF-etched 3.3 66.5 30.1 2.209302326 1,000 Å SiO2/Si(100)

The TOF-SIMS spectra for the ‘SC-1 cleaned, HF-etched’ 1,000 Å SiO₂ andthe ‘as-received’ 1,000 Å SiO₂ samples are shown in FIG. 35 . It isclear from the spectra in FIG. 35 that there is a much higher surfacecoverage of passivating species on the “SC-1 cleaned, HF-etched” 1,000 ÅSiO₂ woo) sample relative to the ‘as-received’ 1,000 Å SiO₂ sample.

Normalized ion intensities for positive ions with mass 45 amu, 29 amu,43 amu, 59 amu and 73 amu or “SC-1 cleaned, HF-etched” 1,000 ÅSiO₂/Si(100) and ‘as-received’ 1,000 Å SiO₂ samples are presented in thetable below.

Thermal Sample Treatment mass 45 amu mass 29 amu mass 43 amu mass 59 amumass 73 amu As-Received 1,000 Å No 554 355 564 133.3 241.7 SiO2/Si(100)SC-1 Cleaned, HF-etched No 727 349 610 150.3 307 1,000 Å SiO2/Si(100)

Example 21 (Comparative): Formation of tri-n-propylsilyl SurfacePassivation on ‘SC-1 Cleaned’, 1,000 Å SiO₂/Si(100) and “as-Received”1,000 Å SiO₂/Si(100) Using ClSi(CH₂CH₂CH₃)₃ (tri-n-propyl chlorosilane)at 445° C.

The “SC-1 cleaned” 1,000 Å SiO₂ samples were subjected to the “SC-1”cleaning process previously described prior to the formation of thepassivation layer. A tri-n-propylsilyl passivation layer was thenselectively formed on the “SC-1 cleaned” 1,000 Å SiO₂ samples and the“as-received” 1,000 Å SiO₂/Si(100) samples using the following process.The ‘as-received’ samples were not cleaned.

Several of the ‘SC-1 cleaned’, 1000 Å SiO₂ and ‘as-received’, 1,000 ÅSiO₂/Si(100) samples were then loaded into the tube of a tube furnacereactor system under a flow of 250 sccm ultra-high purity N₂ gas at roomtemperature with as minimum a delay as possible. The tube was thensealed and slowly evacuated to a pressure of 30 mTorr. A flow of 20 sccmN₂ was then introduced into the reactor tube and a reduced pressure N₂purge was conducted for 2 minutes (at a pressure of 2.3 Torr). The flowof N₂ was then stopped and the tube was evacuated to a pressure of ≤5mTorr. The previously described cycle purging steps were repeated untilthe base pressure of the system was achieved.

After base pressure was achieved, a flow of 20 sccm of ultra-high purityN₂ was introduced into the reactor system and a reduced pressure N₂purge (at 2.3 Torr) was conducted for 1 hour to reduce the backgroundmoisture concentration in the system prior to initiating the thermaltreatment. As known to those skilled in the art, use of a load locksystem will enable greatly reduced cycle times while still providing therequired system purity for the processes described herein to beoperative.

Under a flow of 20 sccm ultra-high purity N₂ through the tube at apressure of 2.5 Torr while the sample temperature was raised to 445° C.The samples were equilibrated at 445° C. for 10 minutes, the N₂ flow wasterminated and the tube was fully evacuated to a pressure of no morethan 1 mTorr. The tube was then charged with a first chemical dose oftri-n-propyl chlorosilane (CH₃CH₂CH₂)₃SiCl to a pressure of 0.296 Torrand then isolated at this pressure for 6 minutes. The first chemicaldose was then removed from the chamber using a combination of reducedpressure N₂ purging and evacuation that encompassed first introducing adynamic flow of 20 sccm N₂ at a pressure of 2.5 Torr for one minute,followed by evacuation of the tube to a pressure not greater than 10mTorr for one minute. The second chemical dose of (CH₃CH₂CH₂)₃SiCl wasthen introduced in a manner identical to the first dose except that thepressure of the second dose was 0.320 Torr. The second dose was thenremoved in the same manner as the first chemical dose prior to theintroduction of the third chemical dose. The third through tenthchemical doses of (CH₃CH₂CH₂)₃SiCl were then introduced in a manneridentical to the first and second doses except that the pressure ofthese doses varied slightly between 0.300 Torr and 0.350 Torr. The thirdthrough eleventh doses were then removed in the same manner as the firstand second chemical doses, completing the selective formation of thetri-n-propylsilyl surface passivation on the ‘SC-1 cleaned’, 1,000 ÅSiO₂ samples and ‘as-received’ 1,000 Å SiO₂ samples.

After the selective passivation formation was completed, the ‘SC-1cleaned, HF-etched’ 1,000 Å SiO₂ and ‘as-received’ 1,000 Å SiO₂ sampleswere cooled to room temperature under a flow of 20 sccm ultra-highpurity N₂ at a pressure of 2.3 Torr. The samples were then unloadedunder a flow of 500 sccm N₂, quickly enclosed in a container and thenstored under N₂.

The ‘SC-1 cleaned’ 1,000 Å SiO₂ and ‘as-received’ 1,000 Å SiO₂ sampleswere characterized using water contact angle measurements. The resultsof these analyses are presented in the table below.

Water Contact Angle Measurements Water Thermal Contact Angle SampleTreatment (Degrees) As-Received 1,000 Å No 72.6 SiO2/Si(100) SC-1Cleaned 1,000 Å No 76.6 SiO2/Si(100)

Example 22 (Comparative): Formation of Trimethylsilyl SurfacePassivation on ‘SC-1 Cleaned’, 1,000 Å SiO₂/Si(100) and “as-Received”1,000 Å SiO₂/Si(100) Using BrSi(CH₃)₃ (Trimethylbromosilane) at 220° C.

The “SC-1 cleaned” 1,000 Å SiO₂ samples were subjected to the “SC-1”cleaning process previously described prior to the formation of thepassivation layer. A trimethylsilyl passivation layer was thenselectively formed on the “SC-1 cleaned” 1,000 Å SiO₂ samples and the“as-received” 1,000 Å SiO₂ samples using the following process. The‘as-received’ samples were not cleaned.

Several of the ‘SC-1 cleaned’, 1000 Å SiO₂ and ‘as-received’, 1,000 ÅSiO₂/(100) samples were loaded into the tube of a tube furnace reactorsystem under a flow of 250 sccm ultra-high purity N₂ gas at roomtemperature with as minimum a delay as possible. The tube was thensealed and slowly evacuated to a pressure of 40 mTorr. A flow of 20 sccmN₂ was then introduced into the reactor tube and a reduced pressure N₂purge was conducted for 2 minutes (at a pressure of 2.3 Torr). The flowof N₂ was then stopped and the tube was evacuated to a pressure of ≤5mTorr. The previously described cycle purging steps were repeated untilthe base pressure of the system was achieved.

After base pressure was achieved, a flow of 20 sccm of ultra-high purityN₂ was introduced into the reactor system and a reduced pressure N₂purge (at 2.3 Torr) was conducted for 1 hour to reduce the backgroundmoisture concentration in the system prior to initiating the thermaltreatment. As known to those skilled in the art, use of a load locksystem will enable greatly reduced cycle times while still providing therequired system purity for the processes described herein to beoperative.

Under a flow of 20 sccm ultra-high purity N₂ through the tube at apressure of 2.5 Torr while the sample temperature was raised to 220° C.The samples were equilibrated at 220° C. for 10 minutes, the N₂ flow wasterminated and the tube was fully evacuated to a pressure of no morethan 1 mTorr. The tube was then charged with a first chemical dose oftrimethylbromosilane (CH₃)₃SiBr to a pressure of 20.5 Torr and thenisolated at this pressure for 10 minutes. The first chemical dose wasthen removed from the chamber using a combination of reduced pressure N₂purging and evacuation that encompassed first introducing a dynamic flowof 20 sccm N₂ at a pressure of 2.5 Torr for one minute, followed byevacuation of the tube to a pressure not greater than 10 mTorr for oneminute. The second chemical dose of (CH₃)₃SiBr was then introduced in amanner identical to the first dose except that the pressure of thesecond dose was 20.5 Torr. The second dose was then removed in the samemanner as the first chemical dose prior to the introduction of the thirdchemical dose. The third dose of (CH₃)₃SiBr were then introduced in amanner identical to the first and second doses except that the pressureof this dose was 19.5 Torr. The third dose was then removed in the samemanner as the first and second chemical doses, completing the selectiveformation of the trimethylsilyl surface passivation on the ‘SC-1cleaned’, 1,000 Å SiO₂ samples and ‘as-received’ 1,000 Å SiO₂ samples.

After the selective passivation formation was completed, the ‘SC-1cleaned, HF-etched’ 1,000 Å SiO₂ and ‘as-received’ 1,000 Å SiO₂ sampleswere cooled to room temperature under a flow of 20 sccm ultra-highpurity N₂ at a pressure of 2.3 Torr. The samples were then unloadedunder a flow of 500 sccm N₂, quickly enclosed in a container and thenstored under N₂.

The ‘SC-1 cleaned’ 1,000 Å SiO₂ and ‘as-received’ 1,000 Å SiO₂ sampleswere characterized using water contact angle measurements. The resultsof these analyses are presented in the table below.

Water Contact Angle Measurements Water Thermal Contact Angle SampleTreatment (Degrees) As-Received 1,000 Å No 46.5 SiO2/Si(100) SC-1Cleaned 1,000 Å No 75.9 SiO2/Si(100)

Example 23 (Comparative): Formation of Trimethylsilyl SurfacePassivation on ‘SC-1 Cleaned’, 1,000 Å SiO₂/Si(100) and “as-Received”1,000 Å SiO₂/Si(100) Using ClSi(CH₃)₃ (Trimethylchlorosilane) at 405° C.

The “SC-1 cleaned” 1,000 Å SiO₂ samples were subjected to the “SC-1”cleaning process previously described prior to the formation of thepassivation layer. A trimethylsilyl passivation layer was thenselectively formed on the “SC-1 cleaned” 1,000 Å SiO₂ samples and the“as-received” 1,000 Å SiO₂ samples using the following process. The‘as-received’ samples were not cleaned.

Several of the ‘SC-1 cleaned’, 1000 Å SiO₂ and ‘as-received’, 1,000 ÅSiO₂/(100) samples were loaded into the tube of a tube furnace reactorsystem under a flow of 250 sccm ultra-high purity N₂ gas at roomtemperature with as minimum a delay as possible. The tube was thensealed and slowly evacuated to a pressure of 40 mTorr. A flow of 20 sccmN₂ was then introduced into the reactor tube and a reduced pressure N₂purge was conducted for 2 minutes (at a pressure of 2.3 Torr). The flowof N₂ was then stopped and the tube was evacuated to a pressure of ≤5mTorr. The previously described cycle purging steps were repeated untilthe base pressure of the system was achieved.

After base pressure was achieved, a flow of 20 sccm of ultra-high purityN₂ was introduced into the reactor system and a reduced pressure N₂purge (at 2.3 Torr) was conducted for 1 hour to reduce the backgroundmoisture concentration in the system prior to initiating the thermaltreatment. As known to those skilled in the art, use of a load locksystem will enable greatly reduced cycle times while still providing therequired system purity for the processes described herein to beoperative.

Under a flow of 20 sccm ultra-high purity N₂ through the tube at apressure of 2.5 Torr while the sample temperature was raised to 405° C.The samples were equilibrated at 405° C. for 10 minutes, the N₂ flow wasterminated and the tube was fully evacuated to a pressure of no morethan 1 mTorr. The tube was then charged with a first chemical dose oftrimethylchlorosilane (CH₃)₃SiCl to a pressure of 3.35 Torr and thenisolated at this pressure for 5 minutes. The first chemical dose wasthen removed from the chamber using a combination of reduced pressure N₂purging and evacuation that encompassed first introducing a dynamic flowof 20 sccm N₂ at a pressure of 2.5 Torr for one minute, followed byevacuation of the tube to a pressure not greater than 10 mTorr for oneminute. The second chemical dose of (CH₃)₃SiCl was then introduced in amanner identical to the first dose except that the pressure of thesecond dose was 24.7 Torr. The second dose was then removed in the samemanner as the first chemical dose prior to the introduction of the thirdchemical dose. The third dose of (CH₃)₃SiBr were then introduced in amanner identical to the first and second doses except that the pressureof this dose was 1.9 Torr and the exposure time was 10 minutes. Thethird dose was then removed in the same manner as the first and secondchemical doses, completing the selective formation of the trimethylsilylsurface passivation on the ‘SC-1 cleaned’, 1,000 Å SiO₂ samples and‘as-received’ 1,000 Å SiO₂ samples.

After the selective passivation formation was completed, the ‘SC-1cleaned, HF-etched’ 1,000 Å SiO₂ and ‘as-received’ 1,000 Å SiO₂ sampleswere cooled to room temperature under a flow of 20 sccm ultra-highpurity N₂ at a pressure of 2.3 Torr. The samples were then unloadedunder a flow of 500 sccm N₂, quickly enclosed in a container and thenstored under N₂.

The ‘SC-1 cleaned’ 1,000 Å SiO₂ and ‘as-received’ 1,000 Å SiO₂ sampleswere characterized using water contact angle measurements. The resultsof these analyses are presented in the table below.

Water Contact Angle Measurements Water Thermal Contact Angle SampleTreatment (Degrees) SC-1 Cleaned, 1,000 Å No 65.2 SiO2/Si(100)

Example 24: Formation of Trimethylsilyl Surface Passivation on ‘SC-1Cleaned”, 1,000 Å SiO₂/Si(100) and “as-Received”, 1,000 Å SiO₂/Si(100)Using ISi(CH₃)₃ (Iodotrimethylsilane) at 370° C. with Thermal TreatmentProcessing

Several 1.5″×1.5″ coupons of a 1,000 Å thermal SiO₂/Si(100) [“1,000 ÅSiO₂”) were cleaved from 4″ wafers, blown off with a stream of highpurity nitrogen to remove particles and then loaded into a Teflon boatsuitable for immersion in an SC-1 cleaning bath. The boat and sampleswere then immersed in an SC-1 cleaning solution (100 ml ultra-highpurity NH₄OH (28%-30%); 200 ml ultra-high purity H₂O₂ (28-30%); 1000 mldistilled, deionized H₂O) that was pre-heated to a temperature of70+/−5° C. where they were cleaned for 10 minutes. The SC-1 cleaned,1,000 Å SiO₂/Si(100) and Si(100) samples were then removed from thecleaning bath and rinsed of chemicals using three dump rinse cycles ofdistilled, deionized water. The samples were then dried thoroughly usinga source of ultra-high purity N₂ gas that was filtered for particles.

Several of the ‘SC-1 cleaned’, 1000 Å SiO₂ and “as-received”, 1,000 ÅSiO₂/Si(100) samples were then loaded into the tube of a tube furnacereactor system under a flow of 250 sccm ultra-high purity N₂ gas at roomtemperature with as minimum a delay as possible. The tube was thensealed and slowly evacuated to a pressure of 80 mTorr. A flow of 20 sccmN₂ was then introduced into the reactor tube and a reduced pressure N₂purge was conducted for 2 minutes (at a pressure of 2.3 Torr). The flowof N₂ was then stopped and the tube was evacuated to a pressure of ≤5mTorr. The previously described cycle purging steps were repeated untilthe base pressure of the system was achieved.

After base pressure was achieved, a flow of 20 sccm of ultra-high purityN₂ was introduced into the reactor system and a reduced pressure N₂purge (at 2.3 Torr) was conducted for 1 hour to reduce the backgroundmoisture concentration in the system prior to initiating the thermaltreatment. As known to those skilled in the art, use of a load locksystem will enable greatly reduced cycle times while still providing therequired system purity for the processes described herein to beoperative.

The thermal treatment was then performed under a reduced pressure purgeof ultra-high purity N₂ gas (at 2.3 Torr) using the pre-programmedheating process recipe stored on the temperature controller for thefurnace. The heat traces of two independent thermocouples (onerepresenting the external tube temperature—‘wall’ and one representingthe sample temperature) are shown in FIG. 36 .

After the thermal treatment was completed, a flow of 20 sccm ultra-highpurity N₂ was maintained through the tube at a pressure of 2.5 Torrwhile the sample temperature was reduced to 370° C. The samples wereequilibrated at 370° C. for 10 minutes, the N₂ flow was terminated andthe tube was fully evacuated to a pressure of about 1 mTorr. The tubewas then charged with a first chemical dose of iodotrimethylsilane[ISi(CH₃)₃] to a pressure of 20.1 Torr and then isolated at thispressure for 20 minutes. The first chemical dose was then removed fromthe chamber using a combination of reduced pressure N₂ purging andevacuation that encompassed first introducing a dynamic flow of 20 sccmN₂ at a pressure of 2.5 Torr for one minute, followed by evacuation ofthe tube to a pressure not greater than 10 mTorr for one minute. Thesecond chemical dose of [ISi(CH₃)₃] was then introduced in a manneridentical to the first dose except that the pressure of the second dosewas 19.8 Torr. The second dose was then removed in the same manner asthe first chemical dose prior to the introduction of the third chemicaldose. The third chemical dose of [ISi(CH₃)₃] was then introduced in amanner identical to the first and second doses except that the pressureof the third dose was 20.2 Torr. The third chemical dose was thenremoved in the same manner as the first and second chemical doses,completing the selective formation of the trimethylsilyl surfacepassivation on the ‘SC-1 cleaned’, 1,000 Å SiO₂ samples and the‘as-received’, 1000 Å SiO₂ samples.

After the selective passivation formation was completed, the ‘SC-1cleaned’ 1,000 Å SiO₂ and ‘as-received’ 1000 Å SiO₂ samples were cooledto room temperature under a flow of 20 sccm ultra-high purity N₂ at apressure of 2.3 Torr. The samples were then unloaded under a flow of 500sccm N₂, quickly enclosed in a container and then stored under N₂ forshipment to the vendor for analytical characterization of theirproperties.

The ‘SC-1 cleaned’ 1,000 Å SiO₂ and ‘as-received’ 1000 Å SiO₂ sampleswere characterized using water contact angle measurements, Atomic ForceMicroscopy (AFM) and Time-of-Flight Secondary Ion Mass Spectrometry(TOF-SIMS). The results of these analyses are presented in the tablebelow.

Contact Angle Measurements and Surface Roughness Measurements WaterSurface Thermal Contact Angle Roughness Sample Treatment (Degrees) (nm)As-Received 1,000 Å Yes 90 0.62 SiO2/Si(100) SC-1 Cleaned 1,000 Å Yes87.4 0.29 SiO2/Si(100)

The samples were also analyzed by X-Ray Photoelectron Spectroscopy (XPS)and the results are presented in the table below:

Carbon Oxygen Silicon Sample (atomic %) (atomic %) (atomic %) O/Si RatioAs-Received 1,000 Å 4.4 64.4 31.2 2.06 SiO2/Si(100) SC-1 Cleaned,HF-etched 4.8 64.6 30.4 2.13 1,000 Å SiO2/Si(100)

The TOF-SIMS spectra for the ‘SC-1 cleaned, HF-etched’ 1,000 Å SiO₂ andSi(100) samples are shown in FIG. 37 . Referring to FIG. 37 , the lackof observation of the peaks associated with trimethylsilyl surfacepassivation in the Si(100) TOF-SIMS spectrum is evidence that theformation of the passivation layer was limited to the ‘SC-1 cleaned,HF-etched’ 1,000 Å SiO2/Si(100) substrate. That is, the passivation wasformed selectively on the desired surface and not on the Si(100)surface. This conclusion is also supported by the water contact anglemeasurements for the samples and the AFM surface roughness measurementsfor the samples.

Normalized Ion Intensities for positive ions with mass 45 amu, 29 amu,43 amu, 59 amu and 73 amu for “SC-1 cleaned, HF-etched” 1,000 ÅSiO2/Si(100) and Si(100) are shown in the table below.

Thermal Sample Treatment mass 45 amu mass 29 amu mass 43 amu mass 59 amumass 73 amu As-Received 1,000 Å Yes 458 458 652 36.1 523 SiO2/Si(100)SC-1 Cleaned 1,000 Å Yes 391 391 994 57.7 877 SiO2/Si(100)

Example 25: Formation of Trimethylsilyl Surface Passivation on ‘SC-1Cleaned”, 1,000 Å SiO₂/Si(100) and “as-Received”, 1,000 Å SiO₂/Si(100)Using ISi(CH₃)₃ (Iodotrimethylsilane) at 370° C. without ThermalTreatment Processing

Several 1.5″×1.5″ coupons of a 1,000 Å thermal SiO₂/Si(100) [“1,000 ÅSiO₂”) were cleaved from 4″ wafers, blown off with a stream of highpurity nitrogen to remove particles and then loaded into a Teflon boatsuitable for immersion in an SC-1 cleaning bath. The boat and sampleswere then immersed in an SC-1 cleaning solution (100 ml ultra-highpurity NH₄OH (28%-30%); 200 ml ultra-high purity H₂O₂ (28-30%); 1000 mldistilled, deionized H₂O) that was pre-heated to a temperature of70+/−5° C. where they were cleaned for 10 minutes. The SC-1 cleaned,1,000 Å SiO₂/Si(100) and Si(100) samples were then removed from thecleaning bath and rinsed of chemicals using three dump rinse cycles ofdistilled, deionized water. The samples were then dried thoroughly usinga source of ultra-high purity N₂ gas that was filtered for particles.

Several of the ‘SC-1 cleaned’, 1000 Å SiO₂ and “as-received” 1000 Å SiO₂samples were then loaded into the tube of a tube furnace reactor systemunder a flow of 250 sccm ultra-high purity N₂ gas at room temperaturewith as minimum a delay as possible. The tube was then sealed and slowlyevacuated to a pressure of 80 mTorr. A flow of 20 sccm N₂ was thenintroduced into the reactor tube and a reduced pressure N₂ purge wasconducted for 2 minutes (at a pressure of 2.3 Torr). The flow of N₂ wasthen stopped and the tube was evacuated to a pressure of ≤5 mTorr. Thepreviously described cycle purging steps were repeated until the basepressure of the system was achieved.

After base pressure was achieved, a flow of 20 sccm of ultra-high purityN₂ was introduced into the reactor system and a reduced pressure N₂purge (at 2.3 Torr) was conducted for 1 hour to reduce the backgroundmoisture concentration in the system prior to initiating the thermaltreatment. As known to those skilled in the art, use of a load locksystem will enable greatly reduced cycle times while still providing therequired system purity for the processes described herein to beoperative.

Under a flow of 20 sccm ultra-high purity N₂ through the tube at apressure of 2.5 Torr while the sample temperature was raised to 370° C.The samples were equilibrated at 370° C. for 10 minutes, the N₂ flow wasterminated and the tube was fully evacuated to a pressure of no morethan 1 mTorr. The tube was then charged with a first chemical dose ofdimethylaminotrimethylsilane [(CH₃)₂NSi(CH₃)₃] to a pressure of 20.8Torr and then isolated at this pressure for 20 minutes. The firstchemical dose was then removed from the chamber using a combination ofreduced pressure N₂ purging and evacuation that encompassed firstintroducing a dynamic flow of 20 sccm N₂ at a pressure of 2.5 Torr forone minute, followed by evacuation of the tube to a pressure not greaterthan 10 mTorr for two minutes. The second chemical dose of(CH₃)₂NSi(CH₃)₃ was then introduced in a manner identical to the firstdose except that the pressure of the second dose was 21.0 Torr. Thesecond dose was then removed in the same manner as the first chemicaldose prior to the introduction of the third chemical dose. The thirdchemical dose of (CH₃)₂NSi(CH₃)₃ was then introduced in a manneridentical to the first and second doses except that the pressure of thethird dose was 21.4 Torr. The third chemical dose was then removed inthe same manner as the first and second chemical doses, completing theselective formation of the trimethylsilyl surface passivation on the‘SC-1 cleaned, HF-etched’, 1,000 Å SiO₂ samples, but not on the Si(100)samples.

After the selective passivation formation was completed, the ‘SC-1cleaned’ 1,000 Å SiO₂ and “as-received” 1,000 Å SiO₂ samples were cooledto room temperature under a flow of 20 sccm ultra-high purity N₂ at apressure of 2.3 Torr. The samples were then unloaded under a flow of 500sccm N₂, quickly enclosed in a container and then stored under N₂ forshipment to the vendor for analytical characterization of theirproperties.

The ‘SC-1 cleaned, HF-etched’ 1,000 Å SiO₂ and Si(100) samples werecharacterized using water contact angle measurements, Atomic ForceMicroscopy (AFM) and Time-of-Flight Secondary Ion Mass Spectrometry(TOF-SIMS). For comparison, ‘SC-1 cleaned, HF-etched’ 1,000 Å SiO₂samples that did not receive the thermal treatment processing were alsocharacterized in a similar fashion. The results of these analyses arepresented in the table below.

Contact Angle Measurements and Surface Roughness Measurements WaterSurface Thermal Contact Angle Roughness Sample Treatment (Degrees) (nm)As-Received 1,000 Å No 89.8 0.19 SiO2/Si(100) SC-1 Cleaned 1,000 Å No85.1 0.29 SiO2/Si(100)

The samples were also analyzed by X-Ray Photoelectron Spectroscopy (XPS)and the results are presented in the table below.

Carbon Oxygen Silicon Sample (atomic %) (atomic %) (atomic %) O/Si RatioAs-Received 1,000 Å 3.6 66.8 29.6 2.26 SiO2/Si(100) SC-1 Cleaned,HF-etched 4.1 66.1 29.6 2.23 1,000 Å SiO2/Si(100)

The TOF-SIMS spectra for the ‘SC-1 cleaned’ 1,000 Å SiO₂ and“as-received” 1,000 Å SiO₂ samples are shown in FIG. 38 .

Normalized Ion Intensities for positive ions with mass 45 amu, 29 amu,43 amu, 59 amu and 73 amu for “SC-1 cleaned” 1,000 Å SiO₂/Si(100) andSi(100) are listed in the table below.

Thermal Sample Treatment mass 45 amu mass 29 amu mass 43 amu mass 59 amumass 73 amu As-Received 1,000 Å No 239 441 782 46.4 671 SiO2/Si(100)SC-1 Cleaned 1,000 Å No 244 310 1100 65.8 970 SiO2/Si(100)

While the principles of the invention have been described above inconnection with preferred embodiments, it is to be clearly understoodthat this description is made only by way of example and not as alimitation of the scope of the invention.

The invention claimed is:
 1. A method for selectively passivating thesurface of a substrate by vapor phase reaction, wherein the surface ofthe substrate comprises at least a first surface comprising SiO₂ and aninitial concentration of surface hydroxyl groups and a second surfacecomprising SiH, the method comprising the steps of: contacting thesubstrate to a wet chemical composition to obtain a treated substratecomprising an increased concentration of surface hydroxyl groupsrelative to the initial concentration of surface hydroxyl groups;heating the treated substrate at a temperature of from about 200° C. toabout 600° C. and a pressure of from 10-10 Torr to 3000 Torr, whereinthe heating step converts at least a portion of the surface hydroxylgroups on the first surface to surface siloxane groups on the surface ofthe substrate; exposing the substrate, at a temperature equal to orbelow the heating step, to a silicon-containing compound selected fromthe group consisting of Formula I and Formula II:

wherein R¹, R², and R⁴ are each independently selected from H, a C₁ toC₈ linear alkyl group, a branched C₃ to C₈ alkyl group, a C₃ to C₈cyclic alkyl group, a C₃ to C₁₀ heterocyclic group, a C₃ to C₁₀ alkenylgroup, a C₄ to C₈ aryl group, and a C₃ to C₁₀ alkynyl group; R³ isselected from a C₁ to C₁₈ alkyl group, a branched C₃ to C₁₀ alkyl group,a C₄ to C₁₀ heterocyclic group and a C₄ to C₁₀ aryl group; R⁵ isselected from a bond, a C₁ to C₈ linear alkyl group, a branched C₃ to C₈alkyl group, a C₃ to C₈ cyclic alkyl group, a C₃ to C₁₀ heterocyclicgroup, a C₃ to C₁₀ alkenyl group, a C₄ to C₈ aryl group, and a C₃ to C₁₀alkynyl group; X is selected from NR^(a)R^(b), Cl, F, Br, I, —OCH₃, and—OH, wherein R^(a) and R^(b) are each independently selected from H, aC₁ to C₄ linear alkyl group and a C₁-C₄ branched alkyl group; and n andn′ are each independently selected from a number of from 0 to 5, whereinn+n′>1 and <11, wherein the silicon-containing compound reacts with thesurface hydroxyl groups of the first surface to form a silylether-terminated surface and thereby passivate the surface.
 2. Themethod of claim 1 wherein the silicon-containing compound is at leastone compound represented by Formula I.
 3. The method of claim 2 whereinthe compound represented by Formula I is at least one selected from thegroup consisting of iodo tris(3,3,3-trifluoropropyl) silane,dimethylamino tris(3,3,3-trifluoropropyl) silane,[(CF₃CF₂(CH₂)₆(CH₃)₂SiCl], and bromotris(1,1,1-3,3,3-hexafluoro-isopropyl) silane.
 4. The method of claim 1wherein the silicon-containing compound is a compound represented byFormula II.
 5. The method of claim 4 wherein the compound represented byFormula II is selected from the group consisting of1,3-bis-chlorodimethylsilyl(ethane); 1,3-bis-bromodimethylsilyl(ethane);1,3-bis-iododimethylsilyl(ethane);1,3-bis-dimethylamino-dimethylsilyl(ethane);1,3-bis-chlorodimethylsilyl(propane);1,3-bis-bromodimethylsilyl(propane); 1,3-bis-iododimethylsilyl(propane);1,3-bis-dimethylamino-dimethylsilyl(propane);1,3-bis-chlorodimethylsilyl(butane); 1,3-bis-bromodimethylsilyl(butane);1,3-bis-iododimethylsilyl(butane); and1,3-bis-dimethylamino-dimethylsilyl(butane).
 6. The method of claim 1wherein the contacting step is performed at a temperature of from about50° C. to about 100° C.
 7. The method of claim 6 wherein the contactingstep is performed at a temperature of from about 55° C. to about 95° C.8. The method of claim 7 wherein the contacting step is performed at atemperature of from about 60° C. to about 90° C.
 9. The method of claim1 wherein the heating step is performed at a temperature of from about200° C. to about 650° C.
 10. The method of claim 9 wherein the heatingstep is performed at a temperature of from about 300° C. to about 550°C.
 11. The method of claim 10 wherein the heating step is performed at atemperature of from about 400° C. to about 500° C.
 12. The method ofclaim 1 wherein the heating step is performed by first heating thesubstrate to a temperature of less than 200° C. for 5-10 minutes,followed by increasing the temperature to from about 400° C. to about500° C.
 13. The method of claim 1 wherein the wet chemical compositioncomprises at least one selected from the group consisting of acomposition comprising H₂O₂ (28% aq), NH₄O₄ (28-30%, and H₂O, HF(0.01%-5% (aq)), peroxide, and a mixture of H₂SO₄/H₂O₂.
 14. The methodof claim 1 wherein the second surface comprising SiH comprises at leastone selected from the group consisting of a —SiH₃, —SiH₂, and —SiH. 15.The method of claim 1 wherein the second surface comprising SiHcomprises Si(100).
 16. The method of claim 1 wherein the first surfacecomprising SiO₂ comprises at least one selected from the groupconsisting of a —SiH₃, —SiH₂, and —SiH.
 17. The method of claim 1wherein the second surface comprising SiH comprises SiN.
 18. The methodof claim 1 wherein the second surface comprising SiH comprises a metalor metal oxide.
 19. The method of claim 1 wherein the exposing step isconducted at a temperature of between from 150° C. and 500° C.
 20. Themethod of claim 1 wherein the exposing step is conducted at atemperature of between from 150° C. and 450° C.
 21. The method of claim1 wherein the heating of the treated substrate is accomplished in atleast two separate heating steps.
 22. The method of claim 2 wherein thecompound represented by Formula I is at least one selected from thegroup consisting of trimethylsilicon chloride; trimethylsilicon bromide;trimethylsilicon Iodide; dimethylaminotrimethyl silane;ethylmethylaminotrimethyl silane; diethylaminotrimethyl silane;ethylpropylaminotrimethyl silane; di-propylaminotrimethyl silane;ethylisopropylaminotrimethyl silane; di-iso-propylaminotrimethyl silane;di-n-butyltrimethyl silane; di-isobutyltrimethyl silane; anddi-sec-butyltrimethyl silane.
 23. The method of claim 2 wherein thecompound represented by Formula I is at least one selected from thegroup consisting of triethylsilicon chloride; triethylsilicon bromide;triethylsilicon iodide; dimethylaminotriethyl silane;ethylmethylaminotriethyl silane; diethylaminotriethyl silane;ethylpropylaminotriethyl silane; di-propylaminotriethyl silane;ethylisopropylaminotriethyl silane; di-iso-propylaminotriethyl silane;di-n-butyltriethyl silane; di-isobutyltriethyl silane; anddi-sec-butyltriethyl silane.
 24. The method of claim 2 wherein thecompound represented by Formula I is at least one selected from thegroup consisting of tri-n-propylsilicon chloride; tri-n-propylsiliconbromide; tri-n-propylsilicon iodide; dimethylaminotri-n-propyl silane;ethylmethylaminotri-n-propyl silane; diethylaminotri-n-propyl silane;ethylpropylaminotri-n-propylsilane; di-propylaminotri-n-propyl silane;ethylisopropylaminotri-n-propyl silane; anddi-iso-propylaminotri-n-propyl silane.
 25. The method of claim 2 whereinthe compound represented by Formula I is at least one selected from thegroup consisting of tri-isopropylsilicon chloride; tri-isopropylsiliconbromide; tri-isopropylsilicon iodide; dimethylaminotri-isopropyl silane;ethylmethylamino tri-isopropyl silane; diethylamino tri-isopropylsilane; ethylpropylaminotri-isopropyl silane; di-propylaminotri-isopropyl silane; ethylisopropylamino tri-isopropyl silane; anddi-iso-propylamino tri-isopropyl silane.
 26. The method of claim 2wherein the compound represented by Formula I is at least one selectedfrom the group consisting of tri-n-butylsilicon chloride;tri-n-butylsilicon bromide; tri-n-butylsilicon iodide;dimethylaminotri-n-butyl silane; ethylmethylamino tri-n-butyl silane;and diethylamino tri-n-butyl silane.
 27. The method of claim 2 whereinthe compound represented by Formula I is at least one selected from thegroup consisting of tri-isobutylsilicon chloride; tri-isobutylsiliconbromide; tri-isobutylsilicon iodide; dimethylaminotri-isobutyl silane;ethylmethylamino tri-isobutyl silane; and diethylamino tri-isobutylsilane.
 28. The method of claim 2 wherein the compound represented byFormula I is at least one selected from the group consisting oftri-secbutylsilicon chloride; tri-secbutylsilicon bromide;tri-secbutylsilicon iodide; dimethylaminotri-secbutyl silane;ethylmethylamino tri-secbutyl silane; diethylamino tri-secbutyl silane;tri-n-pentylsilicon chloride; tri-n-pentylsilicon bromide;tri-n-pentylsilicon iodide; and dimethylaminotri-n-pentyl silane. 29.The method of claim 2 wherein the compound represented by Formula I isat least one selected from the group consisting ofchloro-tris(3,3,3-trifluoropropyl)silane;bromo-tris(3,3,3-trifluoropropyl)silane;iodo-tris(3,3,3-trifluoropropyl)silane;dimethylamino-tris(3,3,3-trifluoropropyl)silane;ethylmethylamino-tris(3,3,3-trifluoropropyl)silane;diethylamino-tris(3,3,3-trifluoropropyl)silane;ethylpropylamino-tris(3,3,3-trifluoropropyl)silane;di-propylamino-tris(3,3,3-trifluoropropyl)silane;ethylisopropylamino-tris(3,3,3-trifluoropropyl)silane;di-iso-propylamino-tris(3,3,3-trifluoropropyl)silane;chloro-tris(4,4,4-trifluorobutyl)silane;bromo-tris(4,4,4-trifluorobutyl)silane;iodo-tris(4,4,4-trifluorobutyl)silane; anddimethylamino-tris(4,4,4-trifluorobutyl)silane.
 30. The method of claim2 wherein the compound represented by Formula I is at least one selectedfrom the group consisting of octyldimethylsilicon chloride;octyldimethylsilicon bromide; octyldimethylsilicon iodide;dimethylaminooctyldimethyl silane; decyldimethylsilicon chloride;decyldimethylsilicon bromide; decyldimethylsilicon iodide; dimethylaminodecyldimethyl silane; dodecyldimethylsilicon chloride;dodecyldimethylsilicon bromide; dodecyldimethylsilicon iodide;dimethylaminododecyldimethyl silane; hexadecyldimethylsilicon chloride;hexadecyldimethylsilicon bromide; hexadecyldimethylsilicon iodide;dimethylaminohexadecyldimethyl silane; octadecyldimethylsiliconchloride; octadecyldimethylsilicon bromide; octadecyldimethylsiliconiodide; dimethylamino-octadecyldimethyl silane;chlorodimethyl(1H,1H-2H,2H-perfluorooctyl)silane;bromodimethyl(1H,1H-2H,2H-perfluorooctyl)silane;iododimethyl(1H,1H-2H,2H-perfluorooctyl)silane;dimethylaminodimethyl(1H,1H-2H,2H-perfluorooctyl)silane;chlorodimethyl(1H,1H-2H,2H-perfluorodecyl)silane;bromodimethyl(1H,1H-2H,2H-perfluorodecyl)silane;iododimethyl(1H,1H-2H,2H-perfluorodecyl)silane;dimethylamino-dimethyl(1H,1H-2H,2H-perfluorodecyl)silane;chlorodimethyl(1H,1H-2H,2H-perfluorododecyl)silane;bromodimethyl(1H,1H-2H,2H-perfluorododecyl)silane;iododimethyl(1H,1H-2H,2H-perfluorododecyl)silane; anddimethylamino-dimethyl(1H,1H-2H,2H-perfluorododecyl)silane.
 31. A methodof selectively depositing a film on a surface of a substrate wherein thesurface of the substrate comprises at least a first surface comprisingSiO₂ and an initial concentration of surface hydroxyl groups and asecond surface comprising SiH, the method comprising the steps of:contacting the substrate to a wet chemical composition to obtain atreated substrate comprising an increased concentration of surfacehydroxyl groups relative to the initial concentration of surfacehydroxyl groups; heating the treated substrate at a temperature of fromabout 200° C. to about 600° C. and a pressure of from 10-10 Torr to 3000Torr, wherein the heating step converts at least a portion of thesurface hydroxyl groups on the first surface to surface siloxane groupson the surface of the substrate; exposing the substrate, at atemperature equal to or below the heating step, to a silicon-containingcompound selected from the group consisting of Formula I and Formula II:

wherein R¹, R², and R⁴ are each independently selected from H, a C₁ toC₈ linear alkyl group, a branched C₃ to C₈ alkyl group, a C₃ to C₈cyclic alkyl group, a C₃ to C₁₀ heterocyclic group, a C₃ to C₁₀ alkenylgroup, a C₄ to C₈ aryl group, and a C₃ to C₁₀ alkynyl group; R³ isselected from a C₁ to C₁₈ alkyl group, a branched C₃ to C₁₀ alkyl group,a C₄ to C₁₀ heterocyclic group and a C₄ to C₁₀ aryl group; R⁵ isselected from a bond, a C₁ to C₈ linear alkyl group, a branched C₃ to C₈alkyl group, a C₃ to C₈ cyclic alkyl group, a C₃ to C₁₀ heterocyclicgroup, a C₃ to C₁₀ alkenyl group, a C₄ to C₈ aryl group, and a C₃ to C₁₀alkynyl group; X is selected from NR^(a)R^(b), Cl, F, Br, I, —OCH₃, and—OH, wherein R^(a) and R^(b) are each independently selected from H, aC₁ to C₄ linear alkyl group and a C₁-C₄ branched alkyl group; and n andn′ are each independently selected from a number of from 0 to 5, whereinn+n′>1 and <11, wherein the silicon-containing compound reacts with thesurface hydroxyl groups of the first surface to form a silylether-terminated surface and thereby passivate the surface; and exposingthe substrate to one or more deposition precursors to deposit a film onthe second surface selectively over the first surface.
 32. The method ofclaim 31 wherein the silicon-containing compound is a compoundrepresented by Formula I.
 33. The method of claim 32 wherein thecompound represented by Formula I is selected from the group consistingof iodo tris(3,3,3-trifluoropropyl) silane, dimethylaminotris(3,3,3-trifluoropropyl) silane, [(CF₃CF₂(CH₂)₆(CH₃)₂SiCl], and bromotris(1,1,1-3,3,3-hexafluoro-isopropyl) silane.
 34. The method of claim31 wherein the silicon-containing compound is a compound represented byFormula II.
 35. The method of claim 34 wherein the compound representedby Formula II is selected from the group consisting of1,3-bis-chlorodimethylsilyl(ethane); 1,3-bis-bromodimethylsilyl(ethane);1,3-bis-iododimethylsilyl(ethane);1,3-bis-dimethylamino-dimethylsilyl(ethane);1,3-bis-chlorodimethylsilyl(propane);1,3-bis-bromodimethylsilyl(propane); 1,3-bis-iododimethylsilyl(propane);1,3-bis-dimethylamino-dimethylsilyl(propane);1,3-bis-chlorodimethylsilyl(butane); 1,3-bis-bromodimethylsilyl(butane);1,3-bis-iododimethylsilyl(butane); and1,3-bis-dimethylamino-dimethylsilyl(butane).
 36. The method of claim 31wherein the contacting step is performed at a temperature of from about50° C. to about 100° C.
 37. The method of claim 36 wherein thecontacting step is performed at a temperature of from about 55° C. toabout 95° C.
 38. The method of claim 37 wherein the contacting step isperformed at a temperature of from about 60° C. to about 90° C.
 39. Themethod of claim 31 wherein the heating step is performed at atemperature of from about 200° C. to about 650° C.
 40. The method ofclaim 31 wherein the heating step is performed at a temperature of fromabout 300° C. to about 550° C.
 41. The method of claim 40 wherein theheating step is performed at a temperature of from about 400° C. toabout 500° C.
 42. The method of claim 31 wherein the heating step isperformed by first eating the substrate to a temperature of less than200° C. for 5-10 minutes, followed by increasing the temperature to fromabout 400° C. to about 500° C.
 43. The method of claim 31 wherein thewet chemical composition comprises at least one selected from the groupconsisting of a composition comprising H₂O₂ (28% aq), NH₄O₄ (28-30%, andH₂O, HF (0.01%-5% (aq)), peroxide, and a mixture of H₂SO₄/H₂O₂.
 44. Themethod of claim 31 wherein the second surface comprising SiH comprisesat least one selected from the group consisting of a —SiH₃, —SiH₂, and—SiH.
 45. The method of claim 31 wherein the second surface comprisingSiH comprises Si(100).
 46. The method of claim 31 wherein the firstsurface comprising SiO₂ comprises at least one selected from the groupconsisting of a —SiH₃, —SiH₂, and —SiH.
 47. The method of claim 31wherein the second surface comprising SiH comprises SiN.
 48. The methodof claim 31 wherein the second surface comprising SiH comprises a metalor metal oxide.
 49. The method of claim 31 wherein the exposing step isconducted at a temperature of between from 150° C. and 500° C.
 50. Themethod of claim 31 wherein the exposing step is conducted at atemperature of between from 150° C. and 450° C.
 51. The method of claim31 wherein the heating of the treated substrate is accomplished in atleast two separate heating steps.
 52. The method of claim 32 wherein thecompound represented by Formula I is at least one selected from thegroup consisting of trimethylsilicon chloride; trimethylsilicon bromide;trimethylsilicon Iodide; dimethylaminotrimethyl silane;ethylmethylaminotrimethyl silane; diethylaminotrimethyl silane;ethylpropylaminotrimethyl silane; di-propylaminotrimethyl silane;ethylisopropylaminotrimethyl silane; di-iso-propylaminotrimethyl silane;di-n-butyltrimethyl silane; di-isobutyltrimethyl silane; anddi-sec-butyltrimethyl silane.
 53. The method of claim 32 wherein thecompound represented by Formula I is at least one selected from thegroup consisting of triethylsilicon chloride; triethylsilicon bromide;triethylsilicon iodide; dimethylaminotriethyl silane;ethylmethylaminotriethyl silane; diethylaminotriethyl silane;ethylpropylaminotriethyl silane; di-propylaminotriethyl silane;ethylisopropylaminotriethyl silane; di-iso-propylaminotriethyl silane;di-n-butyltriethyl silane; di-isobutyltriethyl silane; anddi-sec-butyltriethyl silane.
 54. The method of claim 32 wherein thecompound represented by Formula I is at least one selected from thegroup consisting of tri-n-propylsilicon chloride; tri-n-propylsiliconbromide; tri-n-propylsilicon iodide; dimethylaminotri-n-propyl silane;ethylmethylaminotri-n-propyl silane; diethylaminotri-n-propyl silane;ethylpropylaminotri-n-propylsilane; di-propylaminotri-n-propyl silane;ethylisopropylaminotri-n-propyl silane; anddi-iso-propylaminotri-n-propyl silane.
 55. The method of claim 32wherein the compound represented by Formula I is at least one selectedfrom the group consisting of tri-isopropylsilicon chloride;tri-isopropylsilicon bromide; tri-isopropylsilicon iodide;dimethylaminotri-isopropyl silane; ethylmethylamino tri-isopropylsilane; diethylamino tri-isopropyl silane; ethylpropylaminotri-isopropylsilane; di-propylamino tri-isopropyl silane; ethylisopropylaminotri-isopropyl silane; and di-iso-propylamino tri-isopropyl silane. 56.The method of claim 32 wherein the compound represented by Formula I isat least one selected from the group consisting of tri-n-butylsiliconchloride; tri-n-butylsilicon bromide; tri-n-butylsilicon iodide;dimethylaminotri-n-butyl silane; ethylmethylamino tri-n-butyl silane;and diethylamino tri-n-butyl silane.
 57. The method of claim 32 whereinthe compound represented by Formula I is at least one selected from thegroup consisting of tri-isobutylsilicon chloride; tri-isobutylsiliconbromide; tri-isobutylsilicon iodide; dimethylaminotri-isobutyl silane;ethylmethylamino tri-isobutyl silane; and diethylamino tri-isobutylsilane.
 58. The method of claim 32 wherein the compound represented byFormula I is at least one selected from the group consisting oftri-secbutylsilicon chloride; tri-secbutylsilicon bromide;tri-secbutylsilicon iodide; dimethylaminotri-secbutyl silane;ethylmethylamino tri-secbutyl silane; diethylamino tri-secbutyl silane;tri-n-pentylsilicon chloride; tri-n-pentylsilicon bromide;tri-n-pentylsilicon iodide; and dimethylaminotri-n-pentyl silane. 59.The method of claim 32 wherein the compound represented by Formula I isat least one selected from the group consisting ofchloro-tris(3,3,3-trifluoropropyl)silane;bromo-tris(3,3,3-trifluoropropyl)silane;iodo-tris(3,3,3-trifluoropropyl)silane;dimethylamino-tris(3,3,3-trifluoropropyl)silane;ethylmethylamino-tris(3,3,3-trifluoropropyl)silane;diethylamino-tris(3,3,3-trifluoropropyl)silane;ethylpropylamino-tris(3,3,3-trifluoropropyl)silane;di-propylamino-tris(3,3,3-trifluoropropyl)silane;ethylisopropylamino-tris(3,3,3-trifluoropropyl)silane;di-iso-propylamino-tris(3,3,3-trifluoropropyl)silane;chloro-tris(4,4,4-trifluorobutyl)silane;bromo-tris(4,4,4-trifluorobutyl)silane;iodo-tris(4,4,4-trifluorobutyl)silane; anddimethylamino-tris(4,4,4-trifluorobutyl)silane.
 60. The method of claim32 wherein the compound represented by Formula I is at least oneselected from the group consisting of octyldimethylsilicon chloride;octyldimethylsilicon bromide; octyldimethylsilicon iodide;dimethylaminooctyldimethyl silane; decyldimethylsilicon chloride;decyldimethylsilicon bromide; decyldimethylsilicon iodide; dimethylaminodecyldimethyl silane; dodecyldimethylsilicon chloride;dodecyldimethylsilicon bromide; dodecyldimethylsilicon iodide;dimethylaminododecyldimethyl silane; hexadecyldimethylsilicon chloride;hexadecyldimethylsilicon bromide; hexadecyldimethylsilicon iodide;dimethylaminohexadecyldimethyl silane; octadecyldimethylsiliconchloride; octadecyldimethylsilicon bromide; octadecyldimethylsiliconiodide; dimethylamino-octadecyldimethyl silane;chlorodimethyl(1H,1H-2H,2H-perfluorooctyl)silane;bromodimethyl(1H,1H-2H,2H-perfluorooctyl)silane;iododimethyl(1H,1H-2H,2H-perfluorooctyl)silane;dimethylaminodimethyl(1H,1H-2H,2H-perfluorooctyl)silane;chlorodimethyl(1H,1H-2H,2H-perfluorodecyl)silane;bromodimethyl(1H,1H-2H,2H-perfluorodecyl)silane;iododimethyl(1H,1H-2H,2H-perfluorodecyl)silane;dimethylamino-dimethyl(1H,1H-2H,2H-perfluorodecyl)silane;chlorodimethyl(1H,1H-2H,2H-perfluorododecyl)silane;bromodimethyl(1H,1H-2H,2H-perfluorododecyl)silane;iododimethyl(1H,1H-2H,2H-perfluorododecyl)silane; anddimethylamino-dimethyl(1H,1H-2H,2H-perfluorododecyl)silane.